Photoenzymatic Hydrosulfonylation for the Stereoselective Synthesis of Chiral Sulfones DOI
Xiaoyang Chen,

Dannan Zheng,

Linye Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 5, 2023

Abstract Chiral sulfones are recurrent motifs in pharmaceuticals and bioactive molecules. Although chemical methods have been developed to afford α‐ or β‐ chiral sulfones, these protocols rely heavily on the pre‐synthesis of structurally complicated starting materials metal complexes. Herein, we described a photoenzymatic approach for radical‐mediated stereoselective hydrosulfonylation. Engineered variants ene reductases provide efficient biocatalysts this transformation, enabling achieve series β‐chiral sulfonyl compounds with high yields (up 92 %) excellent e.r. values 99 : 1).

Language: Английский

Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis DOI
Matthew J. Genzink, Jesse B. Kidd, Wesley B. Swords

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1654 - 1716

Published: Oct. 4, 2021

Asymmetric catalysis is a major theme of research in contemporary synthetic organic chemistry. The discovery general strategies for highly enantioselective photochemical reactions, however, has been relatively recent development, and the variety photoreactions that can be conducted stereocontrolled manner consequently somewhat limited. photocatalysis complicated by short lifetimes high reactivities characteristic photogenerated reactive intermediates; design catalyst architectures provide effective enantiodifferentiating environments these intermediates while minimizing participation uncontrolled racemic background processes proven to key challenge progress this field. This review provides summary chiral structures have studied solution-phase asymmetric photochemistry, including sensitizers, inorganic chromophores, soluble macromolecules. While some photocatalysts are derived from privileged both ground-state transformations, others structural designs unique offer insight into logic required photocatalysis.

Language: Английский

Citations

305
Photocatalysis in the Life Science Industry DOI
Lisa Candish,

Karl D. Collins,

Gemma C. Cook

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

Citations

292
Recent trends in biocatalysis DOI Creative Commons
Dong Yi, Thomas Bayer, Christoffel P. S. Badenhorst

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(14), P. 8003 - 8049

Published: Jan. 1, 2021

Technological developments enable the discovery of novel enzymes, advancement enzyme cascade designs and pathway engineering, moving biocatalysis into an era technology integration, intelligent manufacturing enzymatic total synthesis.

Language: Английский

Citations

282
A General Organocatalytic System for Electron Donor–Acceptor Complex Photoactivation and Its Use in Radical Processes DOI Creative Commons
Eduardo de Pedro Beato, Davide Spinnato, Wei Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(31), P. 12304 - 12314

Published: July 28, 2021

We report herein a modular class of organic catalysts that, acting as donors, can readily form photoactive electron donor-acceptor (EDA) complexes with variety radical precursors. Excitation visible light generates open-shell intermediates under mild conditions, including nonstabilized carbon radicals and nitrogen-centered radicals. The nature the commercially available xanthogenate dithiocarbamate anion organocatalysts offers versatile EDA complex catalytic platform for developing mechanistically distinct reactions, encompassing redox-neutral net-reductive processes. Mechanistic investigations, by means quantum yield determination, established that closed cycle is operational all developed processes, highlighting ability to turn over iteratively drive every cycle. also demonstrate how catalysts' stability method's high functional group tolerance could be advantageous direct functionalization abundant groups, aliphatic carboxylic acids amines, applications in late-stage elaboration biorelevant compounds enantioselective catalysis.

Language: Английский

Citations

167
Stereodivergent atom-transfer radical cyclization by engineered cytochromes P450 DOI
Qi Zhou, M. A. Chin, Yue Fu

et al.

Science, Journal Year: 2021, Volume and Issue: 374(6575), P. 1612 - 1616

Published: Dec. 23, 2021

Naturally occurring enzymes can be a source of unnatural reactivity that molded by directed evolution to generate efficient biocatalysts with valuable activities. Owing the lack exploitable stereocontrol elements in synthetic systems, steering absolute and relative stereochemistry free-radical processes is notoriously difficult asymmetric catalysis. Inspired innate redox properties first-row transition-metal cofactors, we repurposed cytochromes P450 catalyze stereoselective atom-transfer radical cyclization. A set metalloenzymes was engineered impose substantial over addition step halogen rebound these processes, allowing enantio- diastereodivergent This evolvable metalloenzyme platform represents promising solution tame fleeting intermediates for

Language: Английский

Citations

139
Photobiocatalysis for Abiological Transformations DOI
Wesley Harrison, Xiaoqiang Huang, Huimin Zhao

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(8), P. 1087 - 1096

Published: March 30, 2022

Harnessing biocatalysts for novel abiological transformations is a longstanding goal of synthetic chemistry. Combining the merits biocatalysis and photocatalysis allows selective fueled by visible light offers many advantages including new reactivity, high enantioselectivity, greener syntheses, yields. Photoinduced electron or energy transfer enables methodologies that complement conventional two processes offer orthogonal pathways developing reactions. Enzymes are well suited can be tuned directed evolution to exert control over open-shell intermediates, thereby suppressing undesirable reactions delivering chemo- stereoselectivities. Within past decade, combination was mainly focused on exploiting light-regenerated cofactors function native enzymatic activity. However, recent developments have demonstrated unlock new-to-nature Particularly, discovery application strategies poised expand applications photobiocatalysis.In five years, our lab has been studying combinations applied create solve challenges in organic Our efforts expanded combining external photocatalysts with enzymes through construction synergistic cooperative stereoconvergent reduction system consisting photosensitized ene-reductase-catalyzed alkene reduction. Additionally, also extended capability cofactor-dependent photoenzymatic systems include enantioselective bimolecular radical hydroalkylations alkenes irradiating donor-acceptor complexes comprised redox active unnatural substrates.In this Account, we highlight developed group others aim introducing non-natural reactivity enzymes. Presently, achieve repurposing natural photoenzymes, elucidation photoreactivity within enzymes, artificial photoenzymes. By demonstrating successful these achieving transformations, hope spur interest expanding scope photobiocatalytic use extension creation strategies. elucidate intuition synergizing unique capabilities so photobiocatalysis recognized as potential solution difficult

Language: Английский

Citations

137
Combining chemistry and protein engineering for new-to-nature biocatalysis DOI Open Access
David C. Miller, Soumitra V. Athavale, Frances H. Arnold

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(1), P. 18 - 23

Published: Jan. 12, 2022

Language: Английский

Citations

134
Photobiocatalytic Strategies for Organic Synthesis DOI
Megan A. Emmanuel, Sophie G. Bender,

Catherine Bilodeau

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5459 - 5520

Published: April 28, 2023

Biocatalysis has revolutionized chemical synthesis, providing sustainable methods for preparing various organic molecules. In enzyme-mediated most reactions involve molecules operating from their ground states. Over the past 25 years, there been an increased interest in enzymatic processes that utilize electronically excited states accessed through photoexcitation. These photobiocatalytic a diverse array of reaction mechanisms are complementary to one another. This comprehensive review will describe state-of-the-art strategies photobiocatalysis synthesis until December 2022. Apart reviewing relevant literature, central goal this is delineate mechanistic differences between general employed field. We organize based on relationship photochemical step and transformations. The include studies, substrate scopes, protein optimization strategies. By clearly defining mechanistically-distinct chemistry, we hope illuminate future synthetic opportunities area.

Language: Английский

Citations

133
An asymmetric sp3–sp3 cross-electrophile coupling using ‘ene’-reductases DOI
Haigen Fu,

Jingzhe Cao,

Tianzhang Qiao

et al.

Nature, Journal Year: 2022, Volume and Issue: 610(7931), P. 302 - 307

Published: Aug. 11, 2022

Language: Английский

Citations

116
Photoinduced chemomimetic biocatalysis for enantioselective intermolecular radical conjugate addition DOI
Xiaoqiang Huang, Jianqiang Feng, Jiawen Cui

et al.

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(7), P. 586 - 593

Published: May 2, 2022

Language: Английский

Citations

89