Enantioselective Reductive Oligomerization of Carbon Dioxide into l-Erythrulose via a Chemoenzymatic Catalysis

Autor: Sarah Desmons, Pere Clapés, Laure Vendier, Katie Grayson-Steel, Nelson Nuñez-Dallos, Sébastien Bontemps, Régis Fauré, Claire Dumon, John Hurtado
Přispěvatelé: Ministerio de Ciencia e Innovación (España), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Toulouse Biotechnology Institute (TBI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Universidad de los Andes [Bogota] (UNIANDES), Departamento de Química Biológica y Modelización Molecular, Instituto de Química Avanzada de Cataluña IQAC-CSIC, Barcelona, Région Midi-Pyrénées, Ministerio de Ciencia e Innovación (MICIN), Fondo Europeo de Desarrollo Regional (FEDER) (grant RTI2018-094637-B-I00), Programación Conjunta Internacional (PCI2018-092937) : initiative ERA CoBioTech (Tralaminol), ANR-17-CE07-0015,ICC,Cycle de Calvin Inorganic(2017), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Rok vydání: 2021
Předmět:
Zdroj: Journal of the American Chemical Society
Journal of the American Chemical Society, American Chemical Society, 2021, 143 (39), pp.16274-16283. ⟨10.1021/jacs.1c07872⟩
Journal of the American Chemical Society, 2021, 143 (39), pp.16274-16283. ⟨10.1021/jacs.1c07872⟩
Digital.CSIC. Repositorio Institucional del CSIC
instname
ISSN: 0002-7863
1520-5126
Popis: A cell-free enantioselective transformation of the carbon atom of CO2 has never been reported. In the urgent context of transforming CO2 into products of high value, the enantiocontrolled synthesis of chiral compounds from CO2 would be highly desirable. Using an original hybrid chemoenzymatic catalytic process, we report herein the reductive oligomerization of CO2 into C3 (dihydroxyacetone, DHA) and C4 (l-erythrulose) carbohydrates, with perfect enantioselectivity of the latter chiral product. This was achieved with the key intermediacy of formaldehyde. CO2 is first reduced selectively by 4e– by an iron-catalyzed hydroboration reaction, leading to the isolation and complete characterization of a new bis(boryl)acetal compound derived from dimesitylborane. In an aqueous buffer solution at 30 °C, this compound readily releases formaldehyde, which is then involved in selective enzymatic transformations, giving rise either (i) to DHA using a formolase (FLS) catalysis or (ii) to l-erythrulose with a cascade reaction combining FLS and d-fructose-6-phosphate aldolase (FSA) A129S variant. Finally, the nature of the synthesized products is noteworthy, since carbohydrates are of high interest for the chemical and pharmaceutical industries. The present results prove that the cell-free de novo synthesis of carbohydrates from CO2 as a sustainable carbon source is a possible alternative pathway in addition to the intensely studied biomass extraction and de novo syntheses from fossil resources.
We wish to thank the reviewers, whose comments helped to improve the manuscript and in particular the 1H NMR interpretation of compound 3-13C. S.D. thanks Région Midi-Pyrénées and Université Fédérale de Toulouse for a doctoral fellowship. S.B. thanks the ANR programme JCJC “ICC”. C. Bijani is gratefully acknowledged for his help in the simulation of 3-13C. K.G.-S., C.D., and R.F. thank the Carnot 3BCAR (project SUCRES), including the fellowship of K.G.-S. R.F. thanks the Mission for Transversal and Interdisciplinary Initiatives of the CNRS (project CASCADE). We gratefully thank N. Monties, S. Pizzut, and M. Guicherd for technical assistance in HPLC experiments, G. Cioci for assistance in DSF experiments and protein purification, and the ICEO facility dedicated to enzyme screening and discovery, part of the Integrated Screening Platform of Toulouse (PICT, IBiSA). DSF is part of the Integrated Screening Platform of Toulouse (PICT, IBiSA). We thank S. Heux and A. De Simone for the generous gift of a plasmid containing the gene encoding for FLS. J. Durand is gratefully acknowledged for his help in isolating compound 4-13C by semipreparative HPLC. P.C. thanks the Ministerio de Ciencia e Innovación (MICIN), the Fondo Europeo de Desarrollo Regional (FEDER) (grant RTI2018-094637-B-I00), and Programación Conjunta Internacional (PCI2018-092937), through the initiative ERA CoBioTech
Databáze: OpenAIRE
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