Late-stage C–H functionalization offers new opportunities in drug discovery

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 522 - 545

Published: July 13, 2021

Language: Английский

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Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis

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

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Power of Biocatalysis for Organic Synthesis

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(1), P. 55 - 71

Published: Jan. 14, 2021

Biocatalysis, using defined enzymes for organic transformations, has become a common tool in synthesis, which is also frequently applied industry. The generally high activity and outstanding stereo-, regio-, chemoselectivity observed many biotransformations are the result of precise control reaction active site biocatalyst. This achieved by exact positioning reagents relative to each other fine-tuned 3D environment, specific activating interactions between protein, subtle movements catalyst. Enzyme engineering enables one adapt catalyst desired process. A well-filled biocatalytic toolbox ready be used various reactions. Providing nonnatural conditions evolving biocatalysts play with myriad options creating novel transformations thereby opening new, short pathways target molecules. Combining several pot perform reactions concurrently increases efficiency biocatalysis even further.

Language: Английский

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Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

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Biocatalysis making waves in organic chemistry

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 51(2), P. 594 - 627

Published: Dec. 20, 2021

The many waves of biocatalysis have arisen to solve long-standing synthetic challenges. From industrially applied hydrolases enzymes catalysing selective C–C-bond formation, enables new tools access a plethora compounds.

Language: Английский

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Direct excitation strategy for radical generation in organic synthesis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(11), P. 6320 - 6332

Published: Jan. 1, 2021

This tutorial review encompasses the radical generation based on classical methods and photoredox catalysis. It will also focus only demanding visible-light, which involves EDA complex direct photo-excitation strategy.

Language: Английский

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Stereodivergent atom-transfer radical cyclization by engineered cytochromes P450

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

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Photobiocatalysis for Abiological Transformations

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

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Combining chemistry and protein engineering for new-to-nature biocatalysis

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

Published: Jan. 12, 2022

Language: Английский

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Photobiocatalytic Strategies for Organic Synthesis

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

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