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Marti Roger

Ordentlicher Professor FH

Main skills

Ordentlicher Professor FH

Phone: +41 26 429 67 03

Desktop: HEIA_B10.21

Haute école d'ingénierie et d'architecture de Fribourg
Boulevard de Pérolles 80, 1700 Fribourg, CH

Institute
ChemTech - Institut des technologies chimiques

HES-SO Master
Av. de Provence 6, 1007 Lausanne, CH

Faculty
Chimie et sciences de la vie

Main Degree Programme
Master of Science en Life sciences

Competences in synthetic organic chemistry & process chemistry for the preparation/creation/synthesis of functional organic molecules & polymers using innovative synthesis technologies

Roger Marti studied chemistry at the Technikum Winterthur and the ETH Zurich. He completed his PhD with Prof. Dr. D. Seebach at the ETH Zurich. After postdoctoral studies at Sandoz Pharma USA, he spent seven years at Carbogen (Switzerland) active in PRD and scale-up of pharmaceuticals. In 2004, he joined ZHAW in Winterthur/Wädenswil as Professor of Organic Chemistry. Since 2009, he is Professor of Organic Chemistry & Process Chemistry at the HEIA-FR and member of the Institute ChemTech.

BSc HES-SO en Chimie - Haute école d'ingénierie et d'architecture de Fribourg

MSc HES-SO en Life Sciences - HES-SO Master

S01 - Process Chemistry and Development

Cluster Chemistry - Master of Science in Life Sciences MSLS

C3 - Polymer and applications

Ongoing

Public Mask

Role: Co-applicant

Financement: HES-SO

Description du projet :

Développement du filtre d’un masque de protection jetable destiné au grand public en appliquant l’electrospinning d’un polymère biodégradable.

Research team within HES-SO: Charmet Jérôme , Hengsberger Stefan , Marti Roger

Statut: Ongoing

Smart Hydrogels

Role: Collaborator

Financement: HES-SO

Description du projet :

Synthesis and characterization of smart hydrogels for tissue engineering.

Research team within HES-SO: Marti Roger

Partenaires académiques: Stoppini Luc, Hepia

Statut: Ongoing

Completed

NCCR ' Single Atom Catalysis PRD

AGP

Role: Main Applicant

Financement: FR - EIA - Général école Ra&D; SNF

Description du projet : NCCR Catalysis - Ph.D. Project 'Single Atom Catalysis - Industrial Application"

Research team within HES-SO: Marti Roger , Poier Dario

Partenaires académiques: FR - EIA - Institut ChemTech

Durée du projet: 01.09.2020 - 31.08.2024

Montant global du projet: 393'400 CHF

Statut: Completed

New Ecological CONcretes based on low-energy BIO-based artificial Lightweight Aggregates with multifunctional properties

AGP

Role: Co-applicant

Financement: FR - EIA - Général école Ra&D; FR - EIA - Institut iTEC

Description du projet : Building on novel low-energy lightweight aggregates recently developed at iTEC by cold-bonding of local by-products, the proposed project aims to develop new ecological lightweight concretes optimized for the multifunctional requirements of lightweight timber-based construction, as defined within a holistic environmental performance research and development framework.

Research team within HES-SO: Pathé Julien , Zwicky Daia , Robadey Jacques , Gomez-Von Allmen Sophie , Trevisani Sandro , Pignone Danilo , Marti Roger , Jusselme Thomas , Niederhäuser Elena-Lavinia , Serpell Ricardo , Priore Yasmine , Schulthess Lucile , Cau Sonia Anselmina , Ston Julien

Partenaires académiques: FR - EIA - Institut ChemTech; FR - EIA - Institut ENERGY

Durée du projet: 01.05.2021 - 31.08.2023

Montant global du projet: 141'450 CHF

Statut: Completed

Bio-based smart packaging for enhanced preservation of food quality

AGP

Role: Co-applicant

Financement: FR - EIA - Institut iRAP; Horizon 2020

Description du projet : The BIOSMART project proposal has the ambition to develop active and smart bio-based and compostable packages addressing the needs of several food market segments. The knowledge gained from developing the novel packages forms the basis for tailoring performance and functionality to other flexible and rigid food packages in diverse market segments. An holistic ecosystem approach is pursued by offering solutions that bring enhanced performance and acceptable economics to the packaging value chain to facilitate their implementation and large-scale commercialization. Critical issues that differentiate the present packages from the future all-bio-based and compostable ones are enhanced active and smart functionalities that make possible: light weighting, reduced food residues, shelf life monitoring and longer shelf life, easier consumer waste handling, and all this at a competitive cost to the incumbent. The BIOSMART project proposal develops an approach for selectively integrating superhydrophobic surfaces, microencapsulated phase change materials (thermoregulation), barrier coatings, very low cost sensor devices, and new bio-based and active ingredients (anti-microbial, anti-fungal, and antioxidants), into all-bio-based compostable packages. Three generic packaging systems are selected with specific performance needs as defined by current multi-material fossil-fuel based packages (i.e. pouches, terrines and an hybrid carton/thin film tray). The associate life cycle assessments for the different possible scenarios include the economic feasibility as a defining key performance indicator. Ultimately, the gathered developmental knowledge is consolidated in a material selection and package performance simulation Application. It enables through optimization of key performance indicators and representing emulators a quick selection of relevant plastics, packaging composition, and cost.

Research team within HES-SO: Brodard Pierre , Hennebert Jean , Blanchard Lucien , Albergati Luce , Esseiva Julien , Zurbuchen Nicolas , Ayer Baptiste , Koopmans Rudolf , Mavrozoumi Vasiliki , Rychener Lorenz , Marti Roger

Partenaires académiques: FR - EIA - Institut ChemTech; FR - EIA - Institut iCoSys

Durée du projet: 01.04.2017 - 31.10.2021

Montant global du projet: 948'840 CHF

Statut: Completed

Des biocarburants à base de PHA pour une mobilité durable et neutre en CO2

AGP

Role: Main Applicant

Description du projet : Statistic figures for mobility and traffic in 2018 show that cars and leisure activities prevail in passenger transportation. The car is the most common transport means with an average of 10'370 km per year. Each Swiss citizen consumes on average 700 L of fossil fuels yearly and transport accounts for 39% of CO2 emissions of Switzerland. To reduce these emissions, sustainable biofuels are required. Fossil fuels are already blended with biodiesel or bioethanol from renewable resources, but this corresponds to only 3% of total fuel consumption. Furthermore, biofuels production is currently in competition with food sources. Although electro-mobility is emerging, there are still more than 6 million petrol/diesel vehicles in operation in Switzerland - there is an evolution, but not a revolution in the vehicle population. To this end, solutions for sustainable fuels needs to be developed rapidly, which a) can be integrated into the existing infrastructure, b) are CO2-neutral and c) do not compete with food supply. This is where this project comes in: many bacteria naturally accumulate polyhydroxyalkanoate (PHA) in presence of carbon substrate when another nutrient (nitrogen or phosphorus) is limiting growth. We established a bioprocess with microorganisms that are able to produce PHA with up to 80% in the biomass from CO2. We further chemically convert PHA to various biofuel derivatives (yields >90%, scale >100 g). By our approach of depolymerization and/or hydrogenation (from H2 from solar water splitting) we produced biofuels not competing with food & feed sources. The ecologic potential of our new PHA-based biofuel was assessed by a life cycle assessment (LCA) and compared to alternative and existing competing technologies. Test of the new PHA-based biofuels in an engine test bench unveiled the potential of this novel and innovative biofuel production chain. A patent application is pending.

Research team within HES-SO: Pott Julien , Micaux Fabrice , Zinn Manfred , Pilloud Vincent , Dardano Florian , Miserez Florian , Albergati Luce , Nellen Christian , Alber Bastien , Monney Nils , Maruel Frédéric , Sthioul Hervé , Richard Jacques , Hanik Nils , Utsunomia Camila , Amstutz Véronique , Marti Roger

Partenaires académiques: HES-SO Rectorat; VS - Institut Sciences du vivant; hepia inSTI; FR - EIA - Institut ChemTech

Durée du projet: 01.04.2019 - 30.09.2021

Montant global du projet: 270'000 CHF

Statut: Completed

Call 2011 Production d'énergie propre en milieu urbain basé sur la transformation du CO2 en méthanol offrant un biocarburant neutre en CO2 utilisé dans le cadre de la mobilité urbaine et d'une autonomisation énergétique des bâtiments.

AGP

Role: Collaborator

Requérant(e)s: FR - EIA - Institut ChemTech

Financement: HES-SO Rectorat

Description du projet : La transformation du CO2 en méthanol représente une énergie propre renouvelable et facile à stocker, permettant à la Suisse de relever les défis environnementaux et économiques en lien avec la problématique de l'énergie. La solution proposée offre une production de carburant neutre en CO2 pour des applications en milieu urbain (voitures et pompes à chaleur utilisant une pile au méthanol) se basant sur une vision de bâtiments et de familles autonomes du point de vue énergique.

Research team within HES-SO: Dabros Michal , Grèzes Vincent , Favre-Perrod Patrick , Sanglard Pauline , Perruchoud Antoine , Bourrier Hervé , Vorlet Olivier , Naef Olivier , Richard Jacques , Chappuis Thierry , Marti Roger , Amrein Daniel , Mamula Steiner Olimpia , Bourgeois Jean-Pascal , Ropp Julien

Partenaires académiques: IGT; VS - Institut Entrepreneuriat & MANAGEMENT; hepia inSTI; FR - EIA - Institut ChemTech; FR - EIA - Institut ENERGY

Durée du projet: 01.03.2012 - 31.12.2014

Montant global du projet: 780'000 CHF

Statut: Completed

2025

A scalable dynamic cascade flow reactor for challenging continuous heterogeneous processes

Scientific paper ArODES

Kim-Long Diep, Emilie Buchs, Marlies Moser, Finn L. Steinemann, Alain G. Georg, Flavien L. Morel, Michal Dabros, Roger Marti

CHIMIA, 2025, 79, 6, 433-440

Link to the publication

Summary:

Continuous processes (often referred to as flow chemistry) offers multiple advantages over batch processes and are of particular interest for industrial applications as they provide a more direct path towards process intensification, increased safety and efficiency. However, some chemical processes are still challenging to run in a continuous fashion, such as reactions producing fouling, using stoichiometric amounts of solids, or requiring long residence times. For those kinds of reactions, batch approaches are usually preferred even though some processes would still benefit from the advantages inherent to flow. We herein report our testing and development of a scalable continuous flow reactor equipped with active mixing that was designed to handle those challenging continuous processes, such as the continuous formation of a Grignard reagent from a magnesium powder slurry.

Ligand-induced activation of single-atom palladium heterogeneous catalysts for cross-coupling reactions

Scientific paper ArODES

Dario Poier, Oliver Loveday, Marc Eduard Usteri, Dragos Stoian, Núria López, Sharon Mitchell, Roger Marti, Javier Pérez-Ramírez

ACS Nano, 2025, 19, 1, 1424-1432

Link to the publication

Summary:

Single-atom heterogeneous catalysts (SACs) are potential, recoverable alternatives to soluble organometallic complexes for cross-coupling reactions in fine-chemical synthesis. When developing SACs for these applications, it is often expected that the need for ligands, which are essential for organometallic catalysts, can be bypassed. Contrary to that, ligands remain almost always required for palladium atoms stabilized on commonly used functionalized carbon and carbon nitride supports, as the catalysts otherwise show limited activity. Despite this, ligand optimization has received little attention, and their role in activating SACs is poorly understood. Here, we explore the impact of structurally diverse phosphine ligands on the performance of nitrogen-doped carbon supported single-atoms (Pd1@NC) in the Sonogashira–Hagihara (SH) cross-coupling reaction, using X-ray absorption spectroscopy and density functional theory simulations to rationalize the observed trends. Compared to the ligand-free SAC, SH activity is enhanced in almost all ligand-assisted systems, with reactivity varying by up to 8 orders of magnitude depending on the ligand choice. Distinct trends emerge based on the free ligand volume and ligand class. Unlike molecular systems, the electronic effects of phosphine ligands are less significant in SACs due to the modulating influence of the support. Instead, the performance of SAC-ligand systems is governed by a balance between the ligand deformation energy during coordination with metal centers, and their resulting accessibility to cross-coupling reagents. These findings offer key insights into optimizing Pd-SACs by leveraging phosphine ligands to activate metal centers and tailor the 3D environment.

2024

Sustainable one-pot production and scale-up of the new platform chemical diformylxylose (DFX) from agricultural biomass

Scientific paper ArODES

Jeremy S. Luterbacher, Anastasia O. Komarova, Zezhong John Li, Marie J. Jones, Oliver Erni, Fabien Neuenschwander, Juan D. Medrano-Garcia, Guillén-Gosálbez-Gonzalo, François Maréchal, Roger Marti

ACS Sustainable Chemistry & Engineering, 2024, 12, 34, 12879-12889

Link to the publication

Summary:

The large-scale production of platform chemicals from biomass requires efficient, cost-effective, and sustainable methods. Here, we present three one-pot synthesis routes for producing diformylxylose (DFX), a sugar-based solvent and platform chemical, using d-xylose or corncobs as feedstocks. With yields of approximately 80%, these routes were seamlessly scaled from lab to kilogram-scale in a 15 L batch reactor. Techno-economic assessment demonstrates the competitiveness of the proposed methods against fossil- and biobased analogues. Life-cycle analysis shows the potential of these processes to reduce environmental and societal impacts from cradle to gate. At the “end of life”, DFX is demonstrated to be inherently biodegradable. Overall, we present a compelling case study of scaling a novel platform chemical guided by techno-economic and environmental concerns leading to balanced cost-competitiveness and life-cycle sustainability.

Development of lab-scale continuous stirred-tank reactor as flow process tool for oxidation reactions using molecular oxygen

Scientific paper ArODES

Ursina Gnädinger, Dario Poier, Claudio Trombini, Michal Dabros, Roger Marti

Organic Process Research & Development, 2024, 28, 5, 1860-1868

Link to the publication

Summary:

The use of sustainable oxidants is of great interest to the chemical industry, considering the importance of oxidation reactions for the manufacturing of chemicals and society’s growing awareness of its environmental impact. Molecular oxygen (O2), with an almost optimal atom efficiency in oxidation reactions, presents one of the most attractive alternatives to common reagents that are not only toxic in most cases but produce stoichiometric amounts of waste that must be treated. However, fire and explosion safety concerns, especially when used in combination with organic solvents, restrict its easy use. Here, we use state-of-the-art 3D printing and experimental feedback to develop a miniature continuous stirred-tank reactor (mini-CSTR) that enables efficient use of O2 as an oxidant in organic chemistry. Outstanding heat dissipation properties, achieved through integrated jacket cooling and a high surface-to-volume ratio, allow for a safe operation of the exothermic oxidation of 2-ethylhexanal, surpassing previously reported product selectivity. Moving well beyond the proof-of-concept stage, we characterize and illustrate the reactor’s potential in the gas–liquid–solid triphasic synthesis of an endoperoxide precursor of antileishmanial agents. The custom-designed magnetic overhead stirring unit provides improved stirring efficiency, facilitating the handling of suspensions and, in combination with the borosilicate gas dispersion plate, leading to an optimized gas–liquid interface. These results underscore the immense potential that lies within the use of mini-CSTR in sustainable chemistry.

Performance polyamides built on a sustainable carbohydrate core

Scientific paper ArODES

Lorenz P. Manker, Maxime A. Hedou, Clement Broggi, Marie J. Jones, kristoffer Korsten, Kalaiyarasi Puvanenthiran, Yildiz Kupper, Holger Frauenrath, François Marechal, Véronique Michaud, Roger Marti, Michael P. Shaver, Jeremy S. Luterbacher

Nature Sustainability, 2024, 7, 5, 640-651

Link to the publication

Summary:

Sustainably producing plastics with performance properties across a variety of materials chemistries is a major challenge—especially considering that most performance materials use aromatic precursors that are still difficult to source sustainably. Here we demonstrate catalyst-free, melt polymerization of dimethyl glyoxylate xylose, a stabilized carbohydrate that can be synthesized from agricultural waste with 97% atom efficiency, into amorphous polyamides with performances comparable to fossil-based semi-aromatic alternatives. Despite the presence of a carbohydrate core, these materials retain their thermomechanical properties through multiple rounds of high-shear mechanical recycling and could be chemically recycled. Techno-economic and life-cycle analyses suggest selling prices close to those of nylon 66 with a reduction of global warming potential of up to 75%. This work illustrates the versatility of a carbohydrate moiety to impart performance that can compete with that of semi-aromatic polymers across two important materials chemistries.

Up-scaling a sol-gel process for the production of a multi-component xerogel powder

Scientific paper ArODES

Barbara Pföss, Jonathan Caldi, Sutida Jansod, Christophe Allemann, Pierre Brodard, Roger Marti

CHIMIA, 2024, 78, 3, 142-147

Link to the publication

Summary:

A sol-gel process for the synthesis of a multi-component oxide material from the system SiO2-ZrO2-Al2O3underwent optimization and up-scaling. Initially, on a laboratory scale, components including precursors, catalysts, and additives were methodically evaluated to ensure a safe and efficient transition to larger volumes. Subsequently, the equipment for the whole setup of the sol-gel process was strategically selected. Leveraging insights from these optimizations, the process was successfully scaled-up to pilot-scale operation, conducting hydrolysis, condensation reactions, gelation, aging, and drying within a single, integrated conical dryer system for an 80 L batch. A visual test and FTIR spectroscopy were applied for process control and monitoring.

2023

Tunable and biodegradable poly(ester amide)s for disposable facemasks

Scientific paper ArODES

Esteban Alvarez Seoane, Alessandro Cattaneo, Fabien Neuenschwander, Lucien Blanchard, Tatiana Nogueira Matos, Laure Jeandupeux, Gianni Fiorucci, Maryam Tizgadam, Kelly Tran, Pierre-Louis Sciboz, Luce Albergati, Jérôme Charmet, Roger Marti, Stefan Hengsberger

Macromolecular Materials and Engineering, 2300375

Link to the publication

Summary:

The widespread use of disposable facemasks during the COVID-19 pandemic has led to environmental widespread concern due to microplastic pollution. Biodegradable disposable facemasks are a first step to reducing the environmental impact of pandemics. In this paper we present high-performance facemask components based on novel poly(ester amide) (PEA) grades synthesized from bio-sourced materials and processed into non-woven facemask components. PEA based polymers present an excellent compromise between mechanical performance and biodegradability. Importantly, the properties of the PEA can easily be tuned by changing the ratio of the ester and amides, or variation of diol and diacid part. We synthesized seven polymers which we optimized for biodegradability and processability. Among them, two grades combined electrospinning process compatibility with full degradation within 35 days, using a normalized biodegradation test. The ultra-thin filters thus developed were evaluated for performance on a custom-made characterization bench. The filters achieved a microparticle capture efficiency and breathability comparable to commercial filters. Another PEA grade was optimized to reach optimal visco-thermal properties that made it compatible with solvent-free melt-spinning process as demonstrated with continuous fibres production. Overall, our environmentally friendly solution paves the way for the fabrication of high-performance fibres with excellent biodegradability for the next generation facemasks.

Reaction environment design for multigram synthesis via Sonogashira coupling over heterogeneous palladium single-atom catalysts

Scientific paper ArODES

Dario Poier, Dario Faust Akl, Alicia Rodrigues Machado, Georgios Giannakakis, Sharon Mitchell, Gonzalo Guillén-Gosálbez, Roger Marti, Javier Pérez-Ramírez

ACS Sustainable Chemistry & Engineering, 11, 48, 16935-16945

Link to the publication

Summary:

Single-atom heterogeneous catalysts (SACs) attract growing interest in their application in green chemistry and organic synthesis due to their potential for achieving atomic-level precision. These catalysts offer the possibility of achieving selectivity comparable to the traditionally applied organometallic complexes, while enhancing metal utilization and recovery. However, an understanding of SAC performance in organic reactions remains limited to model substrates, and their application as drop-in solutions may not yield optimal activity. Here, we investigate the previously unaddressed influence of the reaction environment, including solvent, base, cocatalyst, and ligand, on the performance of a palladium SAC in Sonogashira–Hagihara cross-couplings. By examining the effects of different solvents using the established criteria, we find that the behavior of the SAC deviates from trends observed with homogeneous catalysts, indicating a distinct interplay between heterogeneous systems and the reaction environment. Our results illustrate the satisfactory performance of SACs in cross-couplings of aryl iodides and acetylenes with electron-withdrawing and -donating groups, while the use of bromides and chlorides remains challenging. Extending the proof-of-concept stage to multigram scale, we demonstrate the synthesis of an intermediate of the anticancer drug Erlotinib. The catalyst exhibits high stability, allowing for multiple reuses, even under noninert conditions. Life-cycle assessment guides the upscaling of the catalyst preparation and quantifies the potential environmental and financial benefits of using the SAC, while also revealing the negligible impact of the PPh3 ligand and CuI cocatalyst. Our results underscore the significant potential of SACs to revolutionize sustainable organic chemistry and highlight the need for further understanding the distinct interplay between their performance and the reaction environment.

Education in flow chemistry

Professional paper ArODES

Christophe Allemann, Roger Marti

Link to the publication

Summary:

Flow chemistry is a growing and promising technology that can be used in research, development, and production. Nowadays, properly trained staff in flow chemistry is lacking in industry. To efficiently work with this technology, a mix of engineering and chemical skills is required. Although, this dual education is well addressed in the chemistry major given at the Haute Ecole d’Ingénierie et d’Architecture de Fribourg, a school of the University of Applied Sciences and Arts, Western Switzerland, the teaching in flow chemistry should be enhanced and reinforced.

Aiming for more sustainable cross-coupling chemistry by employing single-atom catalysis on scale

Professional paper ArODES

Dario Poier, Sharon Mitchell, Victor Tulus, Gonzalo Guillen-Gosalbez, Javier Pérez-Ramirez, Roger Marti

Link to the publication

Summary:

Scaling up syntheses from mg to kg quantities is a complex endeavor. Besides adapting laboratory protocols to industrial processes and equipment and thorough safety assessments, much attention is paid to the reduction of the process’ environmental impact. For processes including transition metal catalyzed steps, e.g. cross-coupling chemistry, this impact strongly depends on the identity of the metal used. As such, a key approach is the replacement of single-use with reusable heterogeneous catalysts. Transition metal single-atom heterogeneous catalysts (SAC), a novel class of catalytic materials, might exhibit all the necessary properties to step up to this task. This article shall discuss current applications of SAC in cross-coupling chemistry from the point of a process chemist and shed light on the NCCR Catalysis contribution to the field. Investigations of the stability-activity-selectivity relationship of SACs in combination with early-stage life-cycle assessments (LCA) of potential processes lay the foundation for large-scale application tailored catalyst synthesis. Ultimately, prevailing challenges are highlighted, which need to be addressed in future research.

2022

Thermal safety and structure-related reactivity investigation of five-membered cyclic sulfamidates

Scientific paper ArODES

Thomas Ferrari, Caitlin Blum, Lara Amini-Rentsch, Pierre Brodard, Michal Dabros, Pascale Hoehn, Aniko Udvarhelyi, Roger Marti, Michaël Parmentier

Organic Process Research Development, 2022, vol. 26, pp. 2614-2623

Link to the publication

Summary:

Five-membered cyclic sulfamidates are very valuable electrophiles in organic synthesis and readily used on a multikilogram scale. However, their thermal degradation is underreported and might lead to unforeseen and undesirable safety events. In addition, ring or nitrogen substitution can have a tremendous influence on cyclic sulfamidate reactivity toward bases and therefore impact the overall safety assessment of a process. An understanding of such behavior is therefore of high importance in the industry while designing a synthetic route, as a change of, e.g., a protecting group can increase the thermal safety of a step on scale. We report herein the thermal degradation investigation as well as the structure-related reactivity exploration of cyclic sulfamidates, including their use in combination with strong bases. The design of a predictive model to rapidly assess the thermal hazard based on collected data and selected molecular descriptors is also presented.

Development, validation, and application of a custom-made mini-reaction calorimeter for thermal safety screening

Scientific paper ArODES

Caitlin Blum, Lara Amini-Rentsch, Thomas Ferrari, Pierre Brodard, Roger Marti, Pascale Hoehn, Michal Dabros, Michaël Parmentier

Organic Process Research Development, 2022, vol. 26, no. 9, pp. 2624-2628

Link to the publication

Summary:

Before scaling up to production, it is of high importance to evaluate the potential of a reaction to lead to an undesired thermal degradation event. The use of a large amount of compounds is usually required for a reliable calorimetry study. In this work, we report the development of a milliliter-scale reaction calorimeter for reaction screening applications. The setup was designed using laboratory equipment and characterized and validated with routine experiments. The results were sufficiently accurate enabling us to observe trends in the measured reaction enthalpies of a family of compounds reacting with strong bases as a function of the compounds' structures.. The use of the microscale tailor-made calorimeter is considered very valuable for potentially highly energetic reactions since reaction calorimetry studies can be performed accurately and safely with small amounts of valuable materials.

Assessing the environmental benefit of palladium-based single-atom heterogeneous catalysts for Sonogashira coupling

Scientific paper ArODES

D. Faust Akl, Dario Poier, D'Angelo S. C., T. P. Auraujo, V. Tulus, O. V. Safonova, S. Mitchell, Roger Marti, G. Guillen-Gosalbez, J. Perez-Ramirez

Green Chemistry, 2022, vol. 24, article no. 6879

Link to the publication

Summary:

The Pd–Cu catalysed Sonogashira coupling of terminal alkynes and aryl halides is a cornerstone synthetic strategy for C–C bond formation. Homogeneous organometallic systems conventionally applied are typically not reusable and require efficient downstream Pd removal steps for product purification, making it challenging to fully recover the precious metal. A holistic cradle-to-gate life cycle assessment (LCA) unveils that process footprint can be improved up to two orders of magnitude from repeated catalyst reuse. New classes of heterogeneous catalysts based on isolated metal atoms (single-atom catalysts, SACs) demonstrate promising potential to synergise the benefits of solid and molecular catalysts for efficient Pd utilisation. Here we show that using Pd atoms anchored on nitrogen-doped carbon permits full recovery of the metal and reuse of the catalyst over multiple cycles. A hybrid process using the Pd-SAC with a homogeneous CuI cocatalyst is more effective than a fully heterogeneous analogue based on a bimetallic Pd–Cu SAC, which deactivates severely due to copper leaching. In some scenarios, the LCA-based metrics demonstrate the footprint of the hybrid homogeneous–heterogeneous catalytic process is leaner than the purely homogeneous counterpart already upon single reuse. Combining LCA with experimental evaluation will be a useful guide to the implementation of solid, reusable catalysts for sustainable organic transformations.

A review of polylactic acid as a replacement material for single-use laboratory components

Scientific paper ArODES

Brian Freeland, Eanna McCarthy, Rengesh Balakrishnan, Samantha Fahy, Adam Boland, Keith D. Rochfort, Michal Dabros, Roger Marti, Susan M. Kelleher, Jennifer Gaughran

Materials, 2022, vol. 15, no. 9, article no. 2989

Link to the publication

Summary:

Every year, the EU emits 13.4 Mt of CO2 solely from plastic production, with 99% of all plastics being produced from fossil fuel sources, while those that are produced from renewable sources use food products as feedstocks. In 2019, 29 Mt of plastic waste was collected in Europe. It is estimated that 32% was recycled, 43% was incinerated and 25% was sent to landfill. It has been estimated that life-sciences (biology, medicine, etc.) alone create plastic waste of approximately 5.5 Mt/yr, the majority being disposed of by incineration. The vast majority of this plastic waste is made from fossil fuel sources, though there is a growing interest in the possible use of bioplastics as a viable alternative for single-use lab consumables, such as petri dishes, pipette tips, etc. However, to-date only limited bioplastic replacement examples exist. In this review, common polymers used for labware are discussed, along with examining the possibility of replacing these materials with bioplastics, specifically polylactic acid (PLA). The material properties of PLA are described, along with possible functional improvements dure to additives. Finally, the standards and benchmarks needed for assessing bioplastics produced for labware components are reviewed.

2021

Multidecagram scale synthesis of an endoperoxide, precursor of anti-malarial and anti-leishmanial agents, via free-radical [2 + 2 + 2] annulation with molecular oxygen

Scientific paper ArODES

Davide Lardani, Roger Marti, Arianna Quintavalla, Marco Lombardo, Claudio Trombini

Organic Process Research Development, 2021, vol. 25, no. 12, pp. 2718-2729

Link to the publication

Summary:

From screening experimental parameters to scaling up, a safe approach is reported for the multidecagram scale preparation of methyl ester of 6,6-dibutyl-3-hydroxy-3-methyl-1,2-dioxane-4-carboxylic acid (7), a flexible common intermediate for the synthesis of a variety of anti-malarial and/or anti-leishmanial compounds. The critical feature of the reaction is the use of a pure oxygen flow under batch conditions using methyl acetoacetate and 2-butyl-1-hexene as reagents, and a mixture of Mn(II) and Mn(III) acetates as catalysts, in acetic acid. Once the best solvent, catalyst loading, temperature, and reaction time in the small-scale procedure (10 mL vial) were defined, the process was adapted up to a 3 L flask, eventually resulting in the production of about 70 g of 7. The developed reaction protocol gives a satisfactory result considering: (i) the inexpensive starting materials used, (ii) the 100% atom economy of the [2 + 2 + 2]-annulation reaction, (iii) the stoichiometric ratio of the two reagents (only oxygen is used in excess) coupled with low catalyst loading, and (iv) the mild conditions adopted. The calorimetric studies allow us to classify this reaction as an inherently safe process. On a larger scale, the possible formation of a flammable vapor mixture in the reactor headspace was minimized using two parallel continuous flows of oxygen and argon, thus ensuring a constant headspace vapor phase renewal.

The 15th Freiburg Symposium :

Scientific paper ArODES

a short review

Urban Jenelten, Roger Marti

CHIMIA, 2021, vol. 75, no. 7/8, pp. 690-691

Link to the publication

Bioplastik

Professional paper ArODES

Roger Marti, Hans-Peter Meyer, Manfred Zinn

satw : technology outlook 2021, 2021, p. 64

Link to the publication

Summary:

Als Bioplastik bezeichnet man Kunststoffe, die entweder aus erneuerbarer Biomasse produziert werden, aber nicht bioabbaubar sind («Agrokunsstoffe»), oder solche, die bioabbaubar sind und entweder aus einem nicht-erneuerbaren Rohstoff wie Erdöl oder auch aus erneuerbarer Biomasse hergestellt werden. Entgegen der weitverbreiteten Meinung gibt es also Bioplastik, der nicht bioabbaubar ist. Aktuell werden jährlich weltweit mehr als 400 Millionen Tonnen Plastik produziert, die potenziell als Mikro- und Nanoplastik die Umwelt belasten. Es gibt aber auch Bioplastik mit aussergewöhnlichen Eigenschaften, der sich nutzbringend einsetzen lässt.

Biobased polyester-amide/cellulose nanocrystal nanocomposites for food packaging

Scientific paper ArODES

Chris Rader, Christoph Weder, Roger Marti

Macromolecular Materials and Engineering, 2021, vol. 306, no. 3

Link to the publication

Summary:

The worldwide plastic waste production is steadily increasing, since the use of polymeric materials continues to rise. One area of particular high plastic consumption is food packaging. Flexible and rigid packaging films are typically made from petrochemical-sourced polymers, which are utilized because of their low cost, ductility, melt-processability, and gas barrier properties, but a major downside is their inability to biodegrade in a reasonable time. Packaging-relevant properties of nanocomposites based on polyester-amides (PEAs) are reported, which are chosen on account of their tunable crystallinity, biobased starting materials, and biodegradability. These polymers are synthesized via melt polycondensation of a building block made from caprolactone and 1,4-diaminobutane, with the addition of 1,4-butanediol and dimethyl adipate. The fraction of the amide segment is varied between 25 and 75 mol%. The oxygen transmission rate (O2TR) drops upon increasing the amide content from 1.6 × 105 to 2.9 × 10−4 cm3 m−2 d−1 on account of increasing crystallinity. In order to improve the gas barrier properties further, nanocomposites of the PEAs and 1–10 wt% cellulose nanocrystals (CNCs) are prepared. These nanocomposites have indeed lower O2TR values than the neat PEAs, with reductions of as much as 50% for a CNC content of 10 wt%.

2020

Melt polycondensation for the synthesis of polyester amides using kneader reactor technology

Scientific paper ArODES

Lucien Blanchard, Chris Rader, Ennio Vanoli, Roger Marti

CHIMIA International Journal for Chemistry, 2020, vol. 74, no. 12, pp. 1024-1025

Link to the publication

Summary:

In this work, we discuss the process development and scale-up of the melt polycondensation of polyester amides from a laboratory scale to kg-scale in a kneader reactor. We identified and optimized the most important critical parameters and produced kg-quantities of polyester amides with Mn up to 25'000 g/mol and reproducible thermal and mechanical properties. The special kneader reactor allows safe and efficient scale-up of polymerisation reactions at high temperature and viscous melts due to good mixing and efficient mass transfer.

The vitamin C analogue 2-O-ß-D-Glucopyranosyl-L-ascorbic acid in rhizomes, stems and leaves of lycium barbarum

Scientific paper ArODES

Carole Bubloz, Isabelle Udrisard, Fabrice Micaux, Umberto Piantini, Lara Amini-Rentsch, Roger Marti, Wilfried Andlauer

CHIMIA International Journal for Chemistry, 2020, vol. 74, no. 10, pp. 828-830

Link to the publication

Summary:

Awareness of health benefits of goji berries coming from their bioactive compounds, mostly antioxidants like ascorbic acid, has grown. Recently, an ascorbic acid analogue from goji berries, the 2-O-β-D-glucopyranosyl-L-ascorbic acid has been reported. In rats, the analogue is absorbed intact and in the form of free vitamin C and consequently has been proposed as a provitamin C. Synthesis of the analogue is demanding and laborious and therefore reliable natural sources are searched. Knowledge concerning the analogue's occurrence in other parts of goji plant is lacking. The aim of this study was to evaluate the contents of 2-O-β-D-glucopyranosyl-L-ascorbic acid in rhizomes, stems and leaves from Lycium barbarum. Rhizomes, stems and leaveswere extracted and the content of 2-O-β-D-glucopyranosyl-L-ascorbic acid and non glucosylated, free ascorbic acid was determined by HPLC-DAD. 2-O-β-D-glucopyranosyl-L-ascorbic acid was found in all goji plant tissues investigated. Based on dry weight, 3.34 mg/100 g were found in the leaves, 4.05 mg/100 g in the stems and up to 12.6 mg/100 g in the rhizomes. Nevertheless, the analogue content in goji berries is much higher (40 to 280 mg/100 g dry weight). The present study confirmed the presence of 2-O-β-D-glucopyranosyl-L-ascorbic acid in rhizomes, stems and leaves of Lycium barbarum. However, their content compared to goji berries is considerably lower.

2019

Materials science at Swiss Universities of Applied Sciences

Scientific paper ArODES

Pierre Brodard, Michal Dabros, Roger Marti, Ennio Vanoli, Manfred Zinn, Urban Frey, Christian Adlhart, Lucy Kind, Franziska Koch, Floriana Burgio, Johan Stenqvist, Sina Saxer, Uwe Pieles, Patrick Shahgaldian, Sebastian Wendeborn

CHIMIA International Journal for Chemistry, 2019, vol. 73, no. 7/8, pp. 645-655

Link to the publication

Summary:

In the Swiss Universities of Applied Sciences, several research institutes are involved in Materials Science, with different approaches and applications fields. A few examples of recent projects from different groups of the University of Applied Sciences and Arts Western Switzerland (HESSO), the Zurich University of Applied Sciences (ZHAW) and the University of Applied Sciences and Arts Northwestern Switzerland (FHNW) are given.

A novel and efficient continuous-flow route to prepare trifluoromethylated N-fused heterocycles for drug discovery and pharmaceutical manufacturing

Scientific paper ArODES

Lara Amini-Rentsch, Ennio Vanoli, Sylvia Richard-Bildstein, Roger Marti, Gianvito Vilé

Industrial Engineering Chemistry Research (I EC research), 2019, vol. 58, no. 24, pp. 10164-10171

Link to the publication

Summary:

Continuous-flow processing has become one of the fastest-growing research areas in chemistry in the last 10 years. Herein we disclose an automated and scalable continuous-flow route for the quick introduction of trifluoromethyl groups on a variety of heterocycles, with application in drug discovery and manufacturing. This involves the direct alkylation-cyclization of amines in the presence of trifluoroacetic acid or anhydride, cheap and readily available CF3-containing building blocks. Compared to traditional batch reactions involving an intermediate purification step, the continuous-flow reactions occurred quickly and at mild conditions, with high yield and broad functional-group tolerance. The practical utility of the method was demonstrated by a gram-scale synthesis and by the estimation of modern green metrics.

2018

4-epi-Isofagomine derivatives as pharmacological chaperones for the treatment of lysosomal diseases linked to ß-galactosidase mutations :

Scientific paper ArODES

improved synthesis and biological investigations

Sophie Front, Sofia Almeida, Vincent Zoete, Julie Charollais-Thoenig, Estelle Gallienne, Céline Marmy, Vincent Pilloud, Roger Marti, Tim Wood, Olivier R. Martin, Stéphane Demotz

Bioorganic Medicinal Chemistry, 2018, vol. 26, no. 20, pp. 5462-5469

Link to the publication

Summary:

(5aR)-5a-C-pentyl-4-epi-isofagomine 1 is a powerful inhibitor of lysosomal β-galactosidase and a remarkable chaperone for mutations associated with GM1-gangliosidosis and Morquio disease type B. We report herein an improved synthesis of this compound and analogs (5a-C-methyl, pentyl, nonyl and phenylethyl derivatives), and a crystal structure of a synthetic intermediate that confirms its configuration resulting from the addition of a Grignard reagent. These compounds were evaluated as glycosidase inhibitors and their potential as chaperones for mutant lysosomal galactosidases determined. Based on these results and on docking studies, the 5-C-pentyl derivative 1 was selected as the optimal structure for further investigations: this compound induces the maturation of mutated β-galactosidase in fibroblasts of a GM1-gangliosidosis patient and promote the decrease of keratan sulfate and oligosaccharide load in patient cells. Compound 1 is clearly capable of restoring β-galactosidase activity and of promoting maturation of the protein, which should result in significant clinical benefit. These properties strongly support the development of compound 1 for the treatment of GM1-gangliosidosis and Morquio disease type B patients harboring β-galactosidase mutations sensitive to pharmacological chaperoning.

Synthesis and structure modification of ionic liquids to optimize their thermoelectric properties

Scientific paper ArODES

Pilar Pérez López, Stefanie Uhl, Edith Laux, Pauline Sanglard, Roger Marti, Herbert Keppner, Ennio Vanoli

Materials today: proceedings, 2018, 5, 1, pp. 10298-10305

Link to the publication

Summary:

Ionic Liquids (IL) are organic salts with melting temperature typically below 100 °C. The unique properties of ionic liquids such as their excellent chemical and thermal stabilities, their low vapor pressure, their important ionic conductivity makes them interesting compounds in material science and especially in thermoelectric generators (TEGs) for medical, pharma, or electronic applications. A big advantage of ILs is the endless number of cation/anion combinations, which allows synthesizing task-specific ionic liquids for TEG applications. This paper describes the synthesis, physical and electrochemical characterization of novel IL for application in thermoelectric generators (TEGs). We discuss the optimization of the chemical structure of IL regarding their thermoelectric properties via a structure-activity relationship approach. The best ionic liquids are the protic ones with a Seebeck coefficient of 570.24 µV/K for methylammonium trifluoroacetate and -1424.56 µV/K for ethylammonium formate.

Development of thermoelectric generator based on ionic liquids for high temperature applications

Scientific paper ArODES

Edith Laux, Stefanie Uhl, Nicolas Gauthier, Laure Jeandupeux, Herbert Keppner, Pilar Pérez López, Pauline Sanglard, Ennio Vanoli, Roger Marti

Materials Today: Proceedings, 2018, Vol. 5, No. 4, pp. 10195-10202

Link to the publication

Summary:

Current, Seebeck-coefficients (SE) and maximal power output (Pmax) of thermoelectric generators using Ionic Liquids (ILs) were measured to determine the optimal temperature window for their use as thermoelectric generators (TEGs) in the range between room temperature (RT) and 300°C. The IL was sandwiched in a thermoelectric cell between a heated and a cooled electrode, allowing temperature-dependent current, voltage, and power-output characterization. Dissolving redox-couples (e.g. I2/I-) enables charge transfer from the IL to the electrode. It was found, that protic ILs degraded irreversibly at 140°C. Aprotic ILs, however, in combination with LiI/I2 redox couples exhibit higher temperature stability being finally limited either by redox-couple-electrode reactions, by temperature-induced redox couple degradation or by reaching at the boiling point at about 280°C. ILs being solid at room temperature could successfully be activated, as soon as at least the hot electrode of the set-up was heated above the melting point (m.p.) of the IL. As a striking observation, the thermo-voltage (linked to the SE) changes the sign as soon as the cold electrode was kept below the m.p. when Ethylammonium tetrafluoroborate (EA BF4) was used. Another IL, Tetrabutylammonium tetrafluoroborate (TBA BF4) exhibited in the full temperature range negative SE as high as 7 mV/K.

One-pot synthesis of trifluoromethylated quinazolin-4(3H)-ones with trifluoroacetic acid as CF3 source

Scientific paper ArODES

Sofia Almeida, Roger Marti, Ennio Vanoli, Stefan Abele, Simone Tortoioli

The Journal of Organic Chemistry (JOC), 2018, 83, 9, pp. 5104-5113

Link to the publication

Summary:

A novel and convenient one-pot sequential cascade method for the preparation of 2-trifluoromethylquinazolin-4(3H)-ones is described. Trifluoroacetic acid (TFA) was employed as inexpensive and readily available CF3 source, which in the presence of T3P was condensed with a variety of anthranilic acids and amines to provide the products in up to 75% yield. The protocol was proved to be robust on 80 g scale, and the synthetic versatility of the prepared quinazolinon-4-ones was demonstrated by derivatization to further useful building blocks.

2017

Continuous processes and flow chemistry at the Universities of Applied Sciences in Switzerland

Scientific paper ArODES

Christophe Allemann, Roger Marti, Olivier Vorlet, Oliver Martin, Peter Riedlberger, Tobias Leonhardt, Angelo Gössi, Wolfgang Riedl, Jean-Manuel Segura, Simon Crelier

CHIMIA International Journal for Chemistry, 2017, vol. 71, no. 7/8, pp. 525-527

Link to the publication

Summary:

This article provides an overview of activities in the fields of continuous processes, flow chemistry and microreactors at the Universities of Applied Sciences in Switzerland.

Continuous Processes and Flow Chemistry at the Universities of Applied Sciences in Switzerland

Scientific paper

Allemann Christophe, Vorlet Olivier, Marti Roger

CHIMIA, 2017 , vol. 71, pp. 525-527

Link to the publication

2016

Universities of Applied Sciences projects at ILMAC and SCS booth

Professional paper ArODES

Roger Marti, David Spichiger

CHIMIA, 2016, vol. 70, no.9, p. 641

Link to the publication

International relations at universities of applied sciences

Professional paper ArODES

Roger Marti, Michal Dabros, Uwe Pieles, Urban Frey, Achim Ecker

CHIMIA International Journal for Chemistry, 2016, vol. 70, no. 7, pp. 555-556

Link to the publication

Summary:

An overview of international relations at the Universities of Applied Sciences in Switzerland is presented.

Daring the challenge and thinking big :

Scientific paper ArODES

the value of early process R&D

Stefan Abele, Jacques-Alexis Funel, Gunther Schmidt, Christian Moessner, Mischa Schwaninger, Roger Marti

CHIMIA International Journal for Chemistry, 2016, vol. 70, no. 7/8, pp. 502-511

Link to the publication

Summary:

The production of the L/T channel blocker ACT-280778 required the enantiomerically pure 5-phenylbicyclo[2.2.2]oct-5-en-2-one (1) as key building block. As the published routes towards 1 are very low yielding (<0.5% yield) and comprise many steps that are not acceptable for scale-up, a series of processes to 1 was developed to match the increasing requirements from first kg-batches to clinical supplies. The three routes are characterized by an individual asset. (1) The first route contains a scale-up of a Diels–Alder reaction with highly reactive reagents and afforded 90 kg enantiomerically pure 1. To mitigate safety risks, a flow reactor was developed for the high-temperature Diels–Alder reaction. This route relied on an efficient enantiomer separation on a ¼-ton scale by HPLC. (2) A Crystallization Induced Diastereomer Transformation (CIDT) during an intramolecular aldol reaction was the pivotal step of a first enantioselective route that starts with the Shibasaki reaction. (3) The 2nd enantioselective route represents a rare example of organocatalysis on scale and allowed to skip six out of nine steps with a significant impact on the cost of goods. This simple way to 1 opened up a short synthesis of Hayashi's chiral diene ligands (bod*) that were so far lacking an affordable access. Some of these novel C1-symmetrical dienes have shown very high enantioselectivities in Rh-catalyzed additions of arylboronates.

4-Epi-Isofagomine Enantiomer Derivatives for the Treatment of Lysosomal Storage Diseases

Scientific paper

Marti Roger, Stefan Demotz, Olivier Martin, Estelle Boivineau, Sophie Front, Julie Charollais-Thoenig, Jean-Pascal Bourgeois, Sofia Almeida

Patent WO2016174131, 2016

Summary:

The present invention relates to 4-epi-isofagomine enantiomer derivatives, pharmaceutically acceptable salts thereof, and the use of said 4-epi-isofagomine enantiomer derivatives in the treatment and/or prevention of lysosomal storage diseases. The present invention is furthermore related to processes for their preparation.

Sandmeyer Prize 2015 - Daring the Challenge and Thinking Big: The Value of Early Process R&D

Scientific paper

Marti Roger, Stefan Abele, Jacques-Alexis Funel, Gunther Schmidt, Christian Moessner, Mischa Schwaninger

CHIMIA, 2016 , vol. 70, pp. 502-511

Link to the publication

Summary:

The production of the L/T channel blocker ACT-280778 required the enantiomerically pure 5-phenylbicyclo[2.2.2]oct-5-en-2-one (1) as key building block. As the published routes towards 1 are very low yielding (<0.5% yield) and comprise many steps that are not acceptable for scale-up, a series of processes to 1 was developed to match the increasing requirements from first kg-batches to clinical supplies. The three routes are characterized by an individual asset. (1) The first route contains a scale-up of a Diels–Alder reaction with highly reactive reagents and afforded 90 kg enantiomerically pure 1. To mitigate safety risks, a flow reactor was developed for the high-temperature Diels–Alder reaction. This route relied on an efficient enantiomer separation on a ¼-ton scale by HPLC. (2) A Crystallization Induced Diastereomer Transformation (CIDT) during an intramolecular aldol reaction was the pivotal step of a first enantioselective route that starts with the Shibasaki reaction. (3) The 2nd enantioselective route represents a rare example of organocatalysis on scale and allowed to skip six out of nine steps with a significant impact on the cost of goods. This simple way to 1 opened up a short synthesis of Hayashi's chiral diene ligands (bod*) that were so far lacking an affordable access. Some of these novel C1-symmetrical dienes have shown very high enantioselectivities in Rh-catalyzed additions of arylboronates.

Continuous Process for Phase-Transfer-Catalyzed Bisalkylation of Cyclopentadiene for the Synthesis of Spiro[2.4]hepta-4,6-diene

Scientific paper

Marti Roger, Ennio Vanoli, Elia Kilcher, Stefan Abele, Sébastien Freymond, Gunther Schmidt

Org. Process Res. Dev., 2016 , vol. 20, pp. 432-439

Link to the publication

Summary:

The transfer of a highly exothermic phase-transfer-catalyzed bisalkylation of cyclopentadiene with 1,2-dichloroethane from batch to continuous mode using standard and widely available laboratory equipment is presented. Besides the optimization of the reaction temperature and residence time, the efficient mixing of the organic phase (cyclopentadiene, 1,2-dichloroethane, and MeBu3NCl) and the aqueous phase (30% NaOH) was studied in detail and optimized by the use of a simple, homemade “PTFE Raschig ring static mixer” consisting of a PTFE tube filled with small pieces cut from the same PFTE tube. A flow set-up with two PTFE Raschig ring static mixers and three residence time units with a three-stage temperature profile allowed the synthesis of highly energetic spiro[2.4]hepta-4,6-diene in a yield of 95% with a productivity of 15 g/h under safe conditions.

2015

12. Freiburger Symposium 2015 :

Scientific paper ArODES

smart solutions in the chemical process & product development – case studies from the chemical industry

Kerstin Bodmann, Roger Marti

CHIMIA, 2015, vol. 69, no. 1, "Supramolecular Chemistry" Pt. 2, pp. 698-707

Link to the publication

PAT at the Universities of Applied Sciences

Scientific paper ArODES

Michal Dabros, Olivier Vorlet, Roger Marti, Wolfgang Riedl, Gerhard Grundler, Aldo Vaccari, Manfred Zinn, Achim Ecker, Christian Hinderling

CHIMIA International Journal of Chemistry, 2015, vol. 69, no. 7/8, pp. 482-484

Link to the publication

Summary:

An overview of activities in the field of Process Analytical Technologies (PAT) at the Universities of Applied Sciences in Switzerland is presented.

Scalable enantioselective synthesis of Fmoc-ß2-serine and Fmoc-ß2-threonine by an organocatalytic Mannich reaction

Scientific paper ArODES

Daniel Meyer, Roger Marti, Dieter Seebach

European Journal of Organic Chemistry, 2015, vol. 2015, no. 22, pp. 4883-4891

Link to the publication

Summary:

The diastereoselective Mannich reaction of functionalized aldehydes, using a phenethylamine-derived iminium precursor, by activation with prolines and prolinol derivatives have been studied. Optimized reaction conditions have been developed, allowing for scale-up and preparation of γ-amino alcohol derivatives on multi-gram scale from β-hydroxypropanal and -butanal, with diastereoselectivites of typically >73:27 and yields of >60 %. After chromatographic diastereoisomer separation, hydrogenolytic debenzylation, enantiomerically pure Fmoc-β2-Ser(tBu)-OH and Fmoc-β2-Thr(tBu)-OH were thus prepared on multi-gram scale in 6 steps and with overall yields of 24 % and 10 %, respectively, starting from commercially available starting compounds.

Continuous process for phase-transfer-catalyzed bisalkylation of cyclopentadiene for the synthesis of spiro[2.4]hepta-4,6-diene

Scientific paper ArODES

Elia Kilcher, Sébastien Freymond, Ennio Vanoli, Roger Marti, Gunther Schmidt, Stefan Abele

Organic Process Research Development, 2016, no. 20, pp. 432-439

Link to the publication

Summary:

Assessment of non-standard reaction conditions for asymmetric 1,3-dipolar organocatalytic cycloaddition of nitrone with a,ß-unsaturated aldehydes

Scientific paper ArODES

Melinda Mojzesová, Mária Meciarová, Ambroz Almássy, Roger Marti, Radovan Sebesta

Chemical Papers, 2015, vol. 69, no.5, pp. 737-746

Link to the publication

Summary:

Non-standard experimental conditions can often enhance organocatalytic reactions considerably. The current study explores the effectiveness of a range of non-standard reaction conditions for the asymmetric organocatalytic 1,3-dipolar cycloaddition of a nitrone with α,β-unsaturated aldehydes. The influence of ionic liquids, high-pressure conditions, ultrasound, microwave irradiation and ballmilling was tested as well as the flow process. Because of the low reactivity of the nitrone and unsaturated aldehydes in the 1,3-dipolar cycloaddition, cycloadducts were isolated in only moderate yields from the majority of experiments. However, high diastereo- and enantioselectivities were observed in ionic liquids under solvent-free conditions and in the flow reactor.

Organocatalytic oxa-Diels–Alder reaction of a,ß-unsaturated ketones under non-classical conditions

Scientific paper ArODES

Melinda Mojzesová, Mária Meciarová, Roger Marti, Radovan Sebesta

New Journal of Chemistry, 2015, vol. 39, no. 4, pp. 2573-2579

Link to the publication

Summary:

Non-classical reaction conditions are compatible with organocatalysis and can often improve reaction course. Oxa-Diels–Alder reaction of acyclic α,β-unsaturated ketones with aldehydes is a challenging transformation that affords valuable pyranone products. Application of microwave irradiation and solvent-free conditions during ball-milling had the best influence on this reaction, in terms of shortened reaction times and increased product yields. Other factors, such as aqueous conditions, ultrasound and flow conditions also bring notable improvements. Unfortunately, a range of chiral organocatalysts provided only small enantioselectivity of the reaction of up to e.r. 63 : 37.

Organocatalytic oxa-Diels–Alder reaction of a,b-unsaturated ketones under non-classical conditions

Scientific paper

Marti Roger, Melinda Mojzesova, Maria Meciarova, Radovan Sebesta

New J. Chem., 2015 , vol. 39, pp. 2573-2579

Link to the publication

Summary:

Assessment of non-standard reaction conditions for asymmetric 1,3-dipolar organocatalytic cycloaddition of nitrone with a,b-unsaturated aldehydes

Scientific paper

Marti Roger, Melinda Mojzesova, Maria Meciarova, Ambroz Almassy, Radovan Sebesta

Chem. Papers, 2015 , vol. 69, pp. 737-746

Link to the publication

Summary:

Non-standard experimental conditions can often enhance organocatalytic reactions considerably.The current study explores the effectiveness of a range of non-standard reaction conditions for theasymmetric organocatalytic 1,3-dipolar cycloaddition of a nitrone withα,β-unsaturated aldehydes.The influence of ionic liquids, high-pressure conditions, ultrasound, microwave irradiation and ball-milling was tested as well as the flow process. Because of the low reactivity of the nitrone andunsaturatedaldehydesinthe1,3-dipolarcycloaddition,cycloadductswereisolatedinonlymoderateyields from the majority of experiments. However, high diastereo- and enantioselectivities wereobserved in ionic liquids under solvent-free conditions and in the flow reactor.

Scalable Enantioselective Synthesis of Fmoc-β2-Serine and Fmoc-β2-Threonine by an Organocatalytic Mannich Reaction

Scientific paper

Marti Roger, Daniel Meyer, Dieter Seebach

Eur. J. Org. Chem., 2015 , pp. 4883-4891

Link to the publication

Summary:

New t-butyl based aspartate protecting groups preventing aspartimide formation in Fmoc SPPS

Scientific paper

Marti Roger, Raymond Behrendt, Simon Huber, Peter White

J. Pept. Sci., 2015 , vol. 21, pp. 680-687

Link to the publication

Summary:

Obtaining homogenous aspartyl-containing peptides via Fmoc/tBu chemistry is often an insurmountable obstacle. A generic solution for this issue utilising an optimised side-chain protection strategy that minimises aspartimide formation would therefore be most desirable. To this end, we developed the following new derivatives: Fmoc-Asp(OEpe)-OH (Epe = 3-ethyl-3-pentyl), Fmoc-Asp(OPhp)-OH (Php = 4-n-propyl-4-heptyl) and Fmoc-Asp(OBno)-OH (Bno = 5-n-butyl-5-nonyl). We have compared their effectiveness against that of Fmoc-Asp(OtBu)-OH and Fmoc-Asp(OMpe)-OH in the well-established scorpion toxin II model peptide variants H-Val-Lys-Asp-Asn/Arg-Tyr-Ile-OH by treatments of the peptidyl resins with the Fmoc removal reagents containing piperidine and DBU at both room and elevated temperatures. The new derivatives proved to be extremely effective in minimising aspartimide by-products in each application.

2014

Efficient and scalable total synthesis of calcitroic acid and its 13C-labeled derivative

Scientific paper ArODES

Daniel Meyer, Lara Rentsch, Roger Marti

RSC Advances, 2014, vol. 4, pp. 32327-32334

Link to the publication

Summary:

Calcitroic acid, the deactivated form of the physiological active vitamin D3 metabolite calcitrol, and its 13C labeled derivative has been synthesized starting from the commercially available Inhoffen-Lythgoe diol in 11 steps with an overall yield of 21%. The key steps in the synthesis were the formation of the C1-homologated nitrile with KCN and K13CN as well as the Horner–Wittig reaction with the ring A phosphine oxide reagent.

Efficient and scalable total synthesis of calcitroic acid and its 13C-labeled derivative

Scientific paper

Marti Roger, Amini-Rentsch Lara, Daniel Meyer

RSC Adv, 2014 , vol. 4, pp. 3232-3233

Link to the publication

Summary:

2013

CO2 capture by ionic liquids :

Scientific paper ArODES

an answer to anthropogenic CO2 emissions ?

Pauline Sanglard, Olivier Vorlet, Roger Marti, Olivier Naef, Ennio Vanoli

CHIMIA, 67, 10, 711

Link to the publication

Summary:

Ionic liquids (ILs) are efficient solvents for the selective removal of CO2 from flue gas. Conventional, offthe-shelf ILs are limited in use to physisorption, which restricts their absorption capacity. After adding a chemical functionality like amines or alcohols, absorption of CO2 occurs mainly by chemisorption. This greatly enhances CO2 absorption and makes ILs suitable for potential industrial applications. By carefully choosing the anion and the cation of the IL, equimolar absorption of CO2 is possible. This paper reviews the current state of the art of CO2 capture by ILs and presents the current research in this field performed at the ChemTech Institute of the Ecole d'Ingénieurs et d'Architectes de Fribourg.

Green synthesis of mono- and disubstituted pyridine via aromatic nucleophilic substitution

Professional paper ArODES

Ennio Vanoli, Roger Marti, Jean-Pascal Bourgeois, Pierre Brodard, Romain Despland, Justine Horner, Fabrice Gallou

CHIMIA, 67, 9, 656-657

Link to the publication

ADIBO-based “Click” chemistry for diagnostic peptide micro-array fabrication :

Scientific paper ArODES

physicochemical and assay characteristics

Denis Prim, Fabien Rebeaud, Vincent Cosandey, Roger Marti, Philippe Passeraub, Marc E. Pfeifer

Molecules, 2013, vol. 18, no. 8, pp. 9833-9849

Link to the publication

Summary:

Several azide-derivatized and fluorescently-labeled peptides were immobilized on azadibenzocyclooctyne (ADIBO)-activated slide surfaces via a strain-promoted alkyne-azide cycloaddition (SPAAC) reaction revealing excellent immobilization kinetics, good spot homogeneities and reproducible fluorescence signal intensities. A myc-peptide micro-array immunoassay showed an antibody limit-of-detection (LOD) superior to a microtiter plate-based ELISA. Bovine serum albumin (BSA) and dextran covalently attached via “click” chemistry more efficiently reduced non-specific binding (NSB) of fluorescently-labeled IgG to the microarray surface in comparison to immobilized hexanoic acid and various types of polyethylene glycol (PEG) derivatives. Confirmation of these findings via further studies with other proteins and serum components could open up new possibilities for human sample and microarray platform-based molecular diagnostic tests.

Energy-related chemical research at the Universities of Applied sciences

Professional paper ArODES

Wolfgang Riedl, Fabian Fischer, Roger Marti, Dominik Brühwiler

CHIMIA International Journal for Chemistry, 2013, vol. 67, no. 7-8, pp. 611-613

Link to the publication

Summary:

An overview of current activities in the field of energy-related chemical research at the Swiss Universities of Applied Sciences is presented.

CO2 Capture by Ionic Liquids – An Answer to Anthropogenic CO2 Emissions?

Scientific paper

Sanglard Pauline, Vorlet Olivier, Marti Roger, Naef Olivier

CHIMIA, 2013 , vol. 67, no 10, pp. 711-718

Link to the publication

ADIBO-Based “Click” Chemistry for Diagnostic Peptide Micro-Array Fabrication: Physicochemical and Assay Characteristics

Scientific paper

Marti Roger, Pfeifer Marc Emil, Prim Denis, Fabien Rebeaud, Vincent Cosandey, Passeraub Philippe,

Molecules, 2013 , vol. 18, pp. 9833-9849

Link to the publication

Summary:

2012

Construction of a peptide microarray for auto-anti-body detection

Scientific paper ArODES

Vincent Cosandey, Fabien Debrot, Jérémy Kaeser, Roger Marti, Philippe Passeraub, Jannick Pétremand, Denis Prim, Marc E. Pfeifer

CHIMIA International Journal for Chemistry, 2012, vol. 66, no. 10, pp. 803-806

Link to the publication

Summary:

Peptide and protein microarrays provide a multiplex approach to identification and quantification of protein–protein interactions (PPI), useful to study for instance antigen–antibody properties. Multivariate serology assays detecting multiple tumor auto-antibodies (TAA) is an emerging class of blood tests for cancer detection. Here we describe the efficient coupling of peptide baits derived from the BRCA1-associated RING domain protein 1 (BARD1) to a solid surface and detection of a commercially available anti-BARD1 antibody with this newly designed peptide microarray. Analytical sensitivity and specificity were shown to be comparable to a microtiter plate based enzyme-linked immunosorbent assay (ELISA).

Microwave barrel reactor use in trimethylolpropane oleate synthesis by Candida antarctica lipase in a biphasic non-solvent process

Scientific paper ArODES

Manuel Happe, Pascal Grand, Sébastien Farquet, Sandrine Aeby, Jean-Claude Héritier, François Corthay, Eric Mabillard, Roger Marti, Ennio Vanoli, Alain-François Grogg, Samuel Nussbaum, Alain Roduit, François Tièche, Sam Salem, Carole Constantin, Esther Schmitt, Silvan Zahno, Christoph Ellert, Ahmed Habib, Julien Wyss, Fabian Fischer

Green Chemistry, 2012, no. 8

Link to the publication

Summary:

A novel microwave barrel reactor (MBR) was constructed and used in lipase catalyzed biolubricant synthesis. The MBR is thought as a versatile process tool for biotransformation and green chemistry that overcomes current size limitations in microwave reactors. A lipase mediated biotransformation in the MBR was compared to a state of the art jacketed reactor with external heat exchanger. Oleic acid and trimethylolpropane converted quantitatively (96%) into biolubricants using microwave induction. The heat dissipation in the MBR was analyzed by thermal imaging and inside thermometry. Conversion rates, rate constants and pseudo reaction orders were in line with conventional processing and no microwave effect was detected. The MBR is a versatile new reactor for non solvent, minimal and common solvent processing in the microwave field. While the subject of investigations was biolubricant synthesis in the MBR, the technology described is of wider potential interest in the field of biomass processing and sustainable chemical manufacture.

Construction of a Peptide Microarray for Auto-antibody Detection

Scientific paper

Marti Roger, Vincent Cosandey, Fabien Debrot, Jérémy Kaeser, Passeraub Philippe, Jannick Pétremand, Prim Denis, Pfeifer Marc Emil

Chimia, 2012 , vol. 66, pp. 803-806

Link to the publication

Summary:

High-Temperature Diels−Alder Reactions: Transfer from Batch to Continuous Mode

Scientific paper

Marti Roger, Stefan Abele, Stefan Höck, Gunther Schmidt, Jacques-Alexis Funel

Org. Process Res. Dev., 2012 , vol. 16, pp. 1114-1120

Link to the publication

Summary:

The transfer of a Diels–Alder reaction of (cyclohexa-1,5-dien-1-yloxy)trimethylsilane 1 with α-acetoxyacrylonitrile 2 and acrylonitrile 8, respectively, from batch to continuous mode is presented, using standard and widely available laboratory equipment. A standard microwave-based system was used as probe for the transfer to flow reactors. Temperature and residence time have been optimized in small coiled-tube reactors and confirmed with two production runs in a flow reactor. The inherent increase in safety caused by the small volumes at high temperatures and the achieved productivity (approximately 100 g/h using acrylonitrile) are offering advantages over the batch mode which suffers from thermokinetic limitations for scale-up.

C1-Symmetric Bicyclo[2.2.2]octa-2,5-diene (bod*) Ligands in Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to Enones and 1,2-Addition to N-[(4-Nitrophenyl)sulfonyl]imines

Scientific paper

Marti Roger, Stefan Abele, Rebecca Brönnimann, Sothys Chun

Helv. Chim. Acta, 2012 , vol. 95, pp. 1809-1817

Link to the publication

Summary:

A set of ten C1-symmetric chiral bicyclo[2.2.2]octa-2,5-dienes (bod*) 2 (Fig.?1) were tested as ligands in Rh-catalyzed arylation reactions. The 1,4-addition of arylboronic acids to cyclohex-2-en-1-one, cyclopent-2-en-1-one, and tert-butyl cinnamate proceeded smoothly with excellent enantioselectivities (up to 99% ee; Tables?1–3). The challenging 1,2-addition of triphenylboroxine to N-[(4-nitrophenyl)sulfonyl]imines yielded the product in high yield and in good enantioselectivity (up to 92% ee; Table?4). Generally, the use of C1-symmetric chiral bod* ligands bearing bulky substituents resulted in lower enantioselectivities, whereas several electron-poor and electron-rich bod* ligands gave higher enantioselectivities than the benchmark ligands reported in literature.

Microwave barrel reactor use in trimethylolpropane oleate synthesis by Candida antarctica lipase in a biphasic non-solvent processa

Scientific paper

Marti Roger, Aeby Sandrine, Fischer Fabian, Manuel Happe, Pascal Grand, Sébastian Farquet, Corthay François, Jean-Claude Hértier, Mabillard Eric, Alain-Francois Grogg, Samuel Nussbaum, Roduit Alain, Tièche François, Sam Salem, Carole Constantin, Esther Schmitt, Zahno Silvan, Ellert Christoph, Ahmed Habib, Julien Wyss

Green Chem., 2012 , vol. 14, pp. 2337-2345

Link to the publication

Summary:

2010

Applications of the Chiral Auxiliaries DIOZ and TRIOZ for Conjugate Additions and Comparison with Other Auxiliaries

Scientific paper

Marti Roger, Dieter Seebach, Albert Beck, Hans-Peter Sprecher, Stefan Pletscher, Manuel Möri, Christoph Gaul, Krystyna Patora-Komisarska, Ekatarina Otchertianova

Helv. Chimica Acta, 2010 , vol. 93, pp. 90-110

Link to the publication

Summary:

A number of N-acryloyl-, N-crotonoyl-, N-(3,3,3-trifluorocrotonoyl)-, N-cinnamoyl-, and N-(3-nitroacryloyl)-4-isopropyl- or -4-phenyl-oxazolidin-2-ones with geminal diphenyl substitution, i.e., 7–15, have been prepared and used for conjugate additions of organocuprate reagents (Me, iPr, Ph, 4-MeOPh) in the β-carbonyl (Table?2) and in the α-carbonyl position (NO2-derivative 11 in Scheme?3). The yields and diastereoselectivities are compared with previously tested enoyl-oxazolidinones (Table?2). Highest diastereoselectivities (>90%) are always observed with the 4-Ph derivatives (Hruby effect). Nitroacryloyl-oxazolidinones and a corresponding phenylmenthol ester undergo less diastereoselective additions (Scheme?3). A 3-(1-methylethyl)-5,5-diphenyloxazolidin-2-one (DIOZ)-derived Li2-enolate-nitronate was also tested for α-carbonyl alkylation (Scheme?4). The X-ray crystal structures of three acryloyl-oxazolidinones and of four adducts are described (Tables?1 and 3), and they serve for configurational assignments and description of the stereochemical courses of the additions and alkylation. Possible applications of the nitro compounds for the preparation of β2-amino acids are discussed (Scheme?2).

Thermal Cleavage of the Fmoc Protection Group

Scientific paper

Marti Roger, Stefan Höck, Rainer Riedl, Marina Simeunovic

Chimia, 2010 , vol. 64, pp. 200-203

Link to the publication

Summary:

The Fmoc protection group is among the most commonly used protection groups for the amino function. A fast method for the thermal deavage of this protection group under base-free conditions without the need for dibenzofulvene scavengers is presented. The advantages of this method include straightforward testability by means of a simple high-temperature NMR experiment, usually high yields, and good selectivity towards the BOC protection group and t-butyl ethers.

2009

Synthesis of a Novel Folic Acid Histidine ()-Conjugate Suitable for Labelling with 99mTc and 188Re

Scientific paper

Marti Roger, Christof Sparr, Urs Michel, Cristina Müller, Roger Schibli, Rudolf Moser, Viola Groehn

Synthesis, 2009 , pp. 787-792

Link to the publication

Summary:

Radiolabeled folate derivatives have the potential to target folate receptor-positive tumor cells for noninvasive diagnosis and therapy. We report the synthesis of a novel γ-folic acid-N τ-histidine conjugate 1 wherein the N τ-histidine is suitable for radiolabeling with isotopes 99mTc (diagnosis) and ¹88Re (therapy). A modular synthetic strategy was applied: N α-Boc-α-carboxy-protected glutamic acid was amidically linked to N τ-(functionalized aminoalkyl)histidine via the γ-carboxy group to form building block 8. Intermediate 8 was coupled to protected pteroic acid to give 1 in two steps in 47% yield. N τ-(Functionalized aminoalkyl)histidine was synthesized by two different routes. The preferred route starting from Boc-His-OMe led in two steps to the N τ-(functionalized aminoalkyl)histidine in 36% yield.

2006

Outsourcing – the Challenge of Science, Speed and Quality

Scientific paper

Marti Roger, Simone Andler-Burzlaff, Jason Bertola

The Role of Organic Synthesis in Early Clinical Drug Development (Ed. S. Caron), J. Wiley & Sons, 2006 , pp. 113-126

Link to the publication

2004

Exploration des liquids ioniques comme nouvelle classe de solvents pour les réaction chimiques

Scientific paper

Marti Roger, Aebischer Jean-Nicolas, Ennio Vanoli, Grégory Corminbeouf

Chimia, 2004 , vol. 58, pp. 753-755

Link to the publication

Summary:

Ionic liquids based on laurylsulfates and tosylates anions were developed and characterized. A Heck reaction (synthesis of trans-ethylcinnamate) was optimized in 1-butyl-3-methyl-imidazolium-tosylate ionic liquid. The recycling of the reaction medium, including the catalyst and the ionic liquid, was carefully studied and the following results were obtained: eleven reactions were performed without further catalyst additions, the average yield was 85% with an average reaction time of 10 h.

First Safe and Practical Synthesis of 2-Amino-8-hydroxyquinoline

Scientific paper

Marti Roger, Thomas Storz, Roland Meier, Patrice Nury, Michael Roeder, Kesheng Zhang

Org. Process Res. Dev., 2004 , vol. 8, pp. 663-665

Link to the publication

Summary:

The first safe and efficient synthesis of the important building block 2-amino-8-hydroxyquinoline (1) is described. Starting from the readily available N-oxide 3 of the cheap bulk chemical 8-hydroxyquinoline (2), the target compound is obtained in a two-step one pot procedure in good overall yield (53−66%) and purity (>98%) on a kilogram scale without chromatography.

1997

Solid Phase Synthesis of beta-Peptides via Arndt-Eistert Homologation of Fmoc-Protected Amino Acid Diazoketones.

Scientific paper

Marti Roger, Konrad Bleicher, Kenneth Bair

Tetrahedron Lett., 1997 , vol. 35, pp. 6145-6148

Link to the publication

Summary:

The solid phase synthesis of β-peptides and β-amino acid containing peptides via Arndt-Eister homologation of Fmoc-protected amino acid diazoketones is described. Syntheses were carried out on Wang, Rink and 2-chlorotrityl resins. Quantitative coupling efficiency gave highly pure compounds as proven by RP-HPLC and MS.

Solid Phase Synthesis via 5-Oxazolidinones. Ring Opening Reactions with Amines and Reaction Monitoring by Single Bead FT-IR Microspectroscopy

Scientific paper

Marti Roger, Mark Jarosinski, Bing Yan

J. Org. Chem., 1997 , vol. 62, pp. 5615-5618

Link to the publication

Summary:

We have demonstrated that the oxazolidinone protection scheme is suitable for side-chain immobilization of Asp and Glu and for “activation” of the α-carboxylic acid. The polymer-bound oxazolidinones underwent a ring-opening reaction with a wide range of primary aliphatic and benzylic amines to give in high yield and high purity Asn, Asp, and Gln amides. We further established single bead FT-IR microspectroscopy as an important and easy to use analytical tool in monitoring reactions on solid support. Especially, the oxazolidinone carbonyl IR band at 1800 cm-1 is a marker that enhances the utility of oxazolidinones as a α-carboxylic protection group on solid support. Additional studies on solid-phase organic synthesis via oxazolidinones are ongoing in order to explore other reactions and strategies to gain entry into the production of peptidomimetic structures

Enhanced Resolution in MAS NMR for Combinatorial Chemistry

Scientific paper

Marti Roger, Mark Jarosinski, Michael Shapiro, Jefferson Chin

Tetrahedron Lett., 1997 , vol. 38, pp. 1333-1336

Link to the publication

Summary:

We have demonstrated the ability to obtain high resolution NMR spectra from samples on resin using J-resolved 2D NMR. Projection of the non-tilted spectrum onto the chemical shift dimension provides enhanced resolution and virtually complete disappearance of the polymer resonances.

1996

Polymer- and Dendrimer-Bound Ti-TADDOLates in Catalytic (and Stoichiometric) Enantioselective Reactions – Are Pentacoordinate Cationic Ti-Complexes the Catalytically Active Species ?–

Scientific paper

Marti Roger, Dieter Seebach, Tobias Hintermann

Helv. Chim. Acta, 1996 , vol. 79, pp. 1710-1740

Link to the publication

Summary:

α,α,α′,α′-Tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs), containing styryl groups either at C(2) of the heterocyclic ring or in the α-position, were prepared in the usual way (18–22, 24, 25). These compounds were copolymerized with styrene and divinylbenzene in a suspension, yielding polymers (33–40, Scheme 3) as beads with a rather uniform particle-size distribution (150–45 μm), swellable in common organic solvents. HOCH2- and BrCH2-substituted TADDOLs were also prepared and used for attachement to Merrifield resin or to dendritic molecules (23, 26–32). The TADDOL moieties in these materials are accessible to form Ti (and Al) complexes (Scheme 4) which can be used as polymer- or dendrimer-bound reagents (stoichiometric) or Lewis acids (catalytic). The reactions studied with these new chiral auxiliaries are: enantioselective nucleophilic additions to aldehydes (of R2Zn and RTi(OCHMe2)3; Scheme 5, Table 1) and to ketones (of LiAlH4, Table 2); enantioselective ring opening of meso-anhydrides (Scheme 6); [4+2] and [3+2] cycloadditions of 3-crotonyl-1,3-oxazolidin-2-one to cyclopentadiene and to (Z)-N-benzylidenephenylamine N-oxide ( → 48, 49, Scheme 7, Tables 3, 4, and Fig. 5). The enantioselectivities reached with most of the polymer-bound or dendritic TADDOL ligands were comparable or identical to those observed with the soluble analogs. The activity of the polymer-bound Lewis acids was only slightly reduced as compared with that encountered under homogeneous conditions. Multiple use of the beads (up to 10 times), without decreased performance, has been demonstrated (Figs. 3 and 4). The poorer selectivity in the Diels-Alder reaction (Scheme 7a), induced by the polymer-bound Cl2Ti-TADDOLate as compared to the soluble one, is taken as an opportunity to discuss the mechanism of this Lewis-acid catalysis, and to propose a cationic, trigonal-bipyramidal complex as the catalytically active species (Fig. 6). It is suggested that similar cations may be involved in other Ti-TADDOLate-mediated reactions as well.

2021

Development of a lab demonstrator to test ionic liquids as phase change materials for energy storage

Conference ArODES

Caitlin Blum, Roger Marti, Jacques Robadey

Proceedings of FTAL Conference 2021 - Sustainable smart cities and regions, 28-29 October 2021, Lugano, Switzerland

Link to the conference

Summary:

Phase change materials (PCMs) are an innovative energy storage concept for buildings. Ionic liquids are a new class of such energy storage materials and we present here a lab-scale prototype for their testing and characterization. The design and construction of this lab-scale heat-exchanger and initial results for three newly developed ionic liquids in the prototype are presented, showing their promising PCM properties.

2018

Catalytic Hydrogenation of CO2-based Ionic Liquids into Methanol – Process Intensification and Optimization

Conference

Marti Roger, Ennio Vanoli, Pauline Sanglard

EuropaCat 2019, 18.10.2018 - 23.08.2019, Aachen

Link to the conference

Summary:

Methanol is recognized today as an important and valuable energy carrier with a high potential in replacing fossil resources [1]. A sustainable and carbon-neutral approach to produce methanol is by hydrogenation of carbon dioxide by using hydrogen from solar water splitting. The challenge of this reaction is that CO2 is a rather inert molecule and typically, high pressure and temperature and the use of expensive catalysts with loadings are needed [2]. Further, a CO2-capture system is needed if one wants to use CO2 from the environment. As shown in Figure 1, we developed a capture method using amines to form CO2-based ionic liquids that can then be further hydrogenated to methanol.

Here, we present our work on the process intensification and optimization of the hydrogenation steps of CO2-based ionic liquids. We discuss our DoE studies on the influence of reaction parameters, optimization of the work-up and isolation of the methanol, and of the scale-up.

References

[1] A. Goeppert, M. Czaun, J.-P. J., G. K. Surya Prakash, G. A. Olah, Chem. Soc. Rev., 2014, 43, 7995.

[2] Q.-W. Song, Z.-H. Zhoua, L.-N. He, Green Chem., 2017, 19, 3707.

Miniaturized Continuous Stirred-tank Reactors – mini-CSTR, a New Process Tool for the Lab

Conference

Marti Roger, Ennio Vanoli, Matthieu Kaehr

Swiss Chemical Society Fall Meeting, 01.10.2018 - 01.10.2018, Lausanne

Summary:

Process intensification, continuous processing and the quest for state-of-the-art and new process tools are the driver for innovation in chemical production. We developed a simple in-house prototype of a miniaturized continuous stirred-tank reactor (mini-CSTR) based on the work by Jensen. The big advantage of this mini-CSTR equipment is that it is possible working with “slow” reaction as well as with suspensions in a continuous mode.

Here, we present our work, which consists in manufacturing and assembling of the mini-CSTR in different designs and materials. The use of this equipment in typical reactions, like the Henry nitro aldol reaction or Grignard reaction, and its comparison and critical discussion with the reactions in batch conditions and micro reactors. And finally, preliminary scale-up runs and costs evaluations of the new mini-CSTRs.

References

Jensen et al., React. Chem. Eng., 2016, 1, 501-507.

Une nouvelle génération de piles à la Haute école d'ingénierie et d'architecture de Fribourg

Conference

Marti Roger

RTS CQFD, 18.07.2018 - 17.08.2021, Fribourg

Link to the conference

Summary:

Durant l'été 2018, Sarah Dirren vous propose de faire le tour de quelques innovations "Made in Switzerland" issues principalement des Hautes écoles spécialisées de Suisse occidentale (HES). Chaque jour, elle vous donne rendez-vous en direct d'un lieu différent à la découverte d'une innovation suisse.

Aujourd'hui, Roger Marti, maître de conférences en chimie organique et professeur à l'Institut ChemTech de Fribourg, nous parle de nouvelles piles capables de récupérer l'énergie du corps pour alimenter des petits dispositifs, comme les montres connectées.

Bioinspired Synthesis of Lignans

Conference

SCS Fall Meeting 2019

Marti Roger, Silvia Brandao, Dardano Florian

Fall Meeting 2019, 03.04.2018 - 03.09.2020, Bern

Summary:

Bioinspired Synthesis of Lignans

The lignans are a large group of polyphenols found in plants. These plant lignans have been shown to be transformed in the gut by microorganisms to physiologically more active and bioavailable mammalian lignans like enterodiol or enterolactone. These phenolic compounds have an interest regarding their antioxidant potential and health benefits of lignans have been linked to the prevention of cardiovascular disease, hypercholesterolemia, and various cancers [1].

Here, we present our work, which is on a bioinspired synthesis of a key intermediate in the synthesis of secoisolariciresinol (SECO), a bis-lactone based on dimerization of ferulic acid. Several synthetic approaches, including biocatalysis [2], were evaluated regarding selectivity, yield and “practicality” on scale. The most promising synthesis was scaled-up to multi-gram scale.

References

[1] R. B. Teponno, S. Kusari, M. Spiteller. Nat. Prod. Rep., 2016, 33, 1044-1092.

[2] O.E. Adelakun et al., J. Mol. Cat. B: Enzymatic 2012, 74, 29–35.

2017

Process Optimization for the Scale-Up of a Ribose-Derivative

Conference

Marti Roger, Pilloud Vincent, Luca Roselli, Céline Marmy, Stéphane Demotz, Julie Charollais

Swiss Chemical Society Fall Meeting, 21.08.2017 - 22.08.2017, Bern

Summary:

Lysosomal storage diseases are a group of inherited metabolic disorders caused by the deficiency of lysosomal functions. Over time, an accumulation of those substrates is observed in patient’s tissues and organs causing irreversible damages like a rapid nerve degeneration and a low life expectancy. Dorphan SA developed a new treatment based on an iminosugar derivative to fight against these Lysosomal storage diseases.

Here, we present our work, which consists in enabling and optimizing the first reactions out of the 11 chemical steps in the synthetic route leading to the active pharmaceutical ingredient. In the course of this work, a DoE was performed to increase the yield of the reactions and get a robust and efficient process. The reactions were further evaluated regarding thermal safety, analytical characterization and costs. A preliminary scale-up run is discussed as well.

References

C. Chevrier et al., Carbohydrate Res. 2011, 346, 1202–1211; J.D. More and N.S. Finney, Org. Letters 2002, 4, 3001-3003.

2016

Smart Cities CO2MeOH – Methanol from CO2

Conference

Marti Roger, Mark McCormick

"Smart Cities" by SwissNex India, 01.09.2016, Bangalore, India

Summary:

Presentation of our work on the transformation of CO2 into methanol by developing innovative CO2 capture system and novel catalytic synthesis for transforming CO2 to methanol. The work is supported by a comprehensive LCA study.

Conclusions:

Carbon dioxide can be selective absorbed to task-specific ionic liquids
Carbon dioxide an be transformed in high yield to methanol
Methanol is a new & innovative energy carrier
The Energy Balance and LCA demonstrate

2015

Dorphan – HEIA-FR: Chemistry and biology challenges in the development of a drug candidate for the treatment of the rare and orphan disease GM1-gangliosidosis

Conference

Strategy, preparation and realization of CTI research projects

Marti Roger, Stephane Demotz

Swiss BiotechTM Innovation Day 2015, 17.03.2015, Zug

Summary:

Morquio type B disease and GM1 gangliosidosis are two rare orphan genetic disorders caused by mutated forms of the lysosomal enzyme betagalactosidase. Enzyme inhibitors of type DO-1 are rescuers of mutated enzymes, as they are often endowed with chaperone activity.

Presentation on the Innosuisse Project on the "Preclinical development of a chaperone molecule for two rare orphan diseases: Morquio type B disease and GM1 gangliosidosis". Discussion of the collaboration of Dorphan with the different partners (HEIA-FR, HES-SO Valais / Wallis, and USZ Universitätsspital Zürich).

Achievements

2022

Synthesis & Application

2022 ; R&D

Collaborateurs: Marti Roger

With our competences in organic synthesis, we have many collaborations with industry and academia to support and develop innovative molecules and applications in life sciences:

We developed an efficient and scalable total synthesis of calcitroic acid and its 13C-labeled derivative to support the Bundesamt für Lebensmittelsicherheit und Veterinärwesen BLV in their monitoring of vitamin D and its metabolites
We established a platform of synthetic hydrogels to support tissue engineering and diagnostic applications within the HES-SO - a prototype for online monitoring of a cancer drug direct at the patient has been completed and tested
With Prof. Kim Do from the Center for Psychiatric Neuroscience at CHUV Lausanne we are working on novel cysteine prodrugs and b-amino acid derivatives to increase the GSH level in the brain in order to reduce the oxidative stress and treat schizophrenia.
With Merck Novabiochem we developed new t-butyl-based aspartate protecting groups preventing aspartimide formation in Fmoc SPPS and supported Merck Novabiochem in the industrialization and commercialization of these new products
Our team is active in the development and scale-up of ionic liquids for CO2 capture, for the use of ionic liquids in thermoelectric generators, and as phase change materials for energy stockage
In a Innosuisse project with Saremco Dental AG, we developed and scaled-up novel dental polymers with highly improved biostability properties. This new dental composite is now on the market.
In the EU project BioSmart we are developing and up-scaling aliphatic biobased poly(ester amide)s as flexible materials for packaging applications (https://biosmart-project.eu/)
In collaboration with Idorsia Pharmaceutical we developed an elegant approach to trifluoromethyated hetereocycles as interesting pharmaceutical building blocks based on cheap trifluoroacetic acid

Flow Chemistry & Synthesis Technologies

2022 ; R&D

Collaborateurs: Marti Roger

For over 10 years, I am active in the field of flow chemistry, using and developing micro reactor systems and studying their industrial application:

Together with Actelion Pharmaceuticals we developed several continuous processes, for example a high temperature Diels-Alder reaction or a phase-transfer-catalyzed alkylation reaction for the synthesis of a pharmaceutical intermediate. This work was rewarded the Sandmeyer Prize 2015 of the Swiss Chemical Society
With Idorsia Pharmaceutical we developed efficient flow chemistry to prepare trifluoromethylated N‑fused heterocycles for drug Discovery and production
We developed an in-house mini CSTR system – the system is very flexible in its design and material, can be used to introduce gases, is equipped with a magnetic coupled overhead stirrer system

Memberships in Boards & Societies

2022 ; R&D

Collaborateurs: Marti Roger

Member of the SCS Board of Directors of the Swiss Chemical Society SCS and President of the Division of Industrial & Applied Chemistry (DIAC)

Member of the SATW topical platform “Chemistry” (from 2017)

Member of the Management committee of COST Action CA18220 “FUR4Sustain” (from 2019)

Editorial Board Member of CHIMIA (from 2009 – 2021), the journal of the Swiss Chemical Society

Member of the

Swiss Chemical Society (from 1993)
American Chemical Society (from 1996)
German Chemical Society (from 2005)
Swiss Process and Chemical Engineers (SGVC, from 2011)
Schweizerischer Verband diplomierter Chemiker FH (SVC, from 2013)

Student Projects

2022 ; R&D

Collaborateurs: Marti Roger

Over the years I have been supervising various student projects, mainly Machelor and Master projects, as well as PhD's as co-supervisor.
Most of these projects are in collaboration with industrial partners and some students were also working in the laboratories of the partner. I also have contacts with foreign universities, University of Bologna & University of Laval (Quebec), where students from my group are carrying out their project.

Overview of projects

Process Chemistry & Scale-up

2022 ; R&D

Collaborateurs: Marti Roger

With my team, we are intensively engaged in process chemistry and scale-up of small molecules for fine chemicals as well as for the pharmaceutical industry. Our proved competences in process chemistry includes the development of new synthetic routes, chemistry enabling, process optimization and safety evaluations. With the unique infrastructure in our labs, we can run reactions up to 200 L and produce kg-quantities:

I am partner in the NCCR “Catalysis” (www.nccr-catalysis.ch/) and participating on the implementation of catalytic processes that enable the flexible production of customizable products from renewable feedstocks. Our activities are in the development of scalable single atom catalyst systems for advanced synthesis application like pharma or agro.
Dorphan SA is a small start-up active in the development of treatment of lysosomal storage diseases. We support them in the preclinical development of their lead compound DO-1, an iminosugar derivative by working on the process development and scale-up of this highly complex molecule. We developed a new shorter synthetic route, did lab enabling and optimization work and scaled the synthesis up to 100 g’s.
For Belenos SA, we studied and optimized the synthesis of graphite oxide. The rather challenging reaction using highly corrosive and “explosive” reagents was further successfully scaled-up to multi-kg scale.
Bloom Renewables we are working on the scale-up and industrialization of the valorisation of lignocellulosic biomass and the development of sustainable xylose-based polyester (Innosuisse project).
Together with the Dr. Fabienne Schwab from the Adolph Merkle Institute (Fribourg) we are developing a scalable synthesis of SiO2 nanoparticles on 100L scale. This nanoparticle will be used as sustainable fertilizer (Innosuisse project).

PEOPLE@HES-SO
Directory and Skills inventory

Marti Roger

Ordentlicher Professor FH

Main skills

Organic Chemistry

Green & Sustainable Chemistry

Process Chemistry

Flow Chemistry

Polymers

Asymmetric Synthesis

Catalysis

Ordentlicher Professor FH

Bioinspired Synthesis of Lignans

PEOPLE@HES-SO Directory and Skills inventory

Marti Roger

Ordentlicher Professor FH

Main skills

Organic Chemistry

Green & Sustainable Chemistry

Process Chemistry

Flow Chemistry

Polymers

Asymmetric Synthesis

Catalysis

Ordentlicher Professor FH

PEOPLE@HES-SO
Directory and Skills inventory