Strategic Use of Visible-Light Photoredox Catalysis in Natural Product Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1717 - 1751

Опубликована: Июль 7, 2021

Recent progress in the development of photocatalytic reactions promoted by visible light is leading to a renaissance use photochemistry construction structurally elaborate organic molecules. Because rich functionality found natural products, studies product total synthesis provide useful insights into functional group compatibility these new methods as well their impact on synthetic strategy. In this review, we examine syntheses published through end 2020 that employ visible-light photoredox catalytic step. To assist someone interested employing steps discussed, review organized largely nature bond formed

Язык: Английский

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Visible‐Light‐Induced Homolysis of Earth‐Abundant Metal‐Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(39), С. 21100 - 21115

Опубликована: Фев. 18, 2021

Abstract The mainstream applications of visible‐light photoredox catalysis predominately involve outer‐sphere single‐electron transfer (SET) or energy (EnT) processes precious metal Ru II Ir III complexes organic dyes with low photostability. Earth‐abundant metal‐based M n L ‐type (M=metal, =polydentate ligands) are rapidly evolving as alternative photocatalysts they offer not only economic and ecological advantages but also access to the complementary inner‐sphere mechanistic modes, thereby transcending their inherent limitations ultrashort excited‐state lifetimes for use effective photocatalysts. generic process, termed visible‐light‐induced homolysis (VLIH), entails formation suitable light‐absorbing ligated metal–substrate (M ‐Z; Z=substrate) that can undergo homolytic cleavage generate n−1 Z . further transformations.

Язык: Английский

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Single Electron Transfer-Induced Redox Processes Involving N-(Acyloxy)phthalimides

ACS Catalysis, Год журнала: 2021, Номер 11(3), С. 1640 - 1683

Опубликована: Янв. 20, 2021

The past decade has witnessed the emergence of N-(acyloxy)phthalimides (NHPI esters) and its derivatives at forefront synthetic methods facilitating construction diverse molecular frameworks from readily available carboxylic acid feedstock. NHPI esters are predisposed to undergo reductive fragmentation via a single electron transfer (SET) process under thermal, photochemical, or electrochemical conditions generate corresponding carbon- nitrogen-centered radicals that participate in multitude transformations forge carbon–carbon carbon–heteroatom bonds. chemistry involving received broad applicability not only well-designed cascade annulations but also medicinal natural product synthesis. This comprehensive Review, broadly categorized according nature bond formation, details progress made this field since initial discovery by providing representative examples with mechanistic details, an emphasis on challenges future directions.

Язык: Английский

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Enantioselective Radical Reactions Using Chiral Catalysts

Chemical Reviews, Год журнала: 2022, Номер 122(6), С. 5842 - 5976

Опубликована: Янв. 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.

Язык: Английский

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Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Год журнала: 2021, Номер 50(19), С. 10836 - 10856

Опубликована: Янв. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Язык: Английский

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General Method for Enantioselective Three-Component Carboarylation of Alkenes Enabled by Visible-Light Dual Photoredox/Nickel Catalysis

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(48), С. 20390 - 20399

Опубликована: Ноя. 19, 2020

A visible-light-promoted photoredox/nickel protocol for the enantioselective three-component carboarylation of alkenes with tertiary and secondary alkyltrifluoroborates aryl bromides is described. This redox-neutral allows facile divergent access to a wide array enantioenriched β-alkyl-α-arylated carbonyls, phosphonates, sulfones in high yields excellent enantioselectivities from readily available starting materials. We also report modular synthesis flurbiprofen analogs piragliatin lead compound demonstrate synthetic utility. Experimental computational mechanistic studies were performed gain insights into mechanism origin chemo- enantioselectivity.

Язык: Английский

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Nickel-catalyzed formation of quaternary carbon centers using tertiary alkyl electrophiles

Chemical Society Reviews, Год журнала: 2021, Номер 50(6), С. 4162 - 4184

Опубликована: Янв. 1, 2021

This review provides a comprehensive summary of recent advances in nickel-catalyzed reactions employing tertiary alkyl electrophiles for the construction quaternary carbon centers.

Язык: Английский

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Direct Enantioselective C(sp³)–H Acylation for the Synthesis of α-Amino Ketones

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(45), С. 19058 - 19064

Опубликована: Окт. 30, 2020

A direct enantioselective acylation of α-amino C(sp3)-H bonds with carboxylic acids has been achieved via the merger transition metal and photoredox catalysis. This straightforward protocol enables cross-coupling a wide range acids, one class feedstock chemicals, readily available N-alkyl benzamides to produce highly valuable ketones in high enantioselectivities under mild conditions. The synthetic utility this method is further demonstrated by gram scale synthesis application late-stage functionalization. provides an unprecedented solution address challenging stereocontrol metallaphotoredox catalysis Mechanistic studies suggest α-C(sp3)-H bond benzamide coupling partner cleavage photocatalytically generated bromine radicals form alkyl radicals, which subsequently engages nickel-catalyzed asymmetric acylation.

Язык: Английский

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Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention

Chemical Society Reviews, Год журнала: 2021, Номер 50(22), С. 12808 - 12827

Опубликована: Янв. 1, 2021

Transition metal-catalysed asymmetric coupling has been established as a robust tool for constructing complex organic molecules. Although this area extensively studied, the development of efficient protocols to construct stereogenic centres with excellent regio- and enantioselectivities is highly desirable remains challenging. Asymmetric transition metal catalysis light intervention provides practical alternative strategy current methods considerably expands synthetic utility result abundant feedstocks mild conditions. This tutorial review comprehensively summarizes recent advances in transition-metal-catalysed reactions intervention; particular, concise analysis substrate scope mechanistic scenarios governing stereocontrol discussed.

Язык: Английский

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Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(11), С. 4168 - 4173

Опубликована: Март 11, 2021

1,3-Dienes are readily available feedstocks that widely used in the laboratory and industry. However, potential of converting 1,3-dienes into value-added products, especially chiral has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve first visible-light-induced, enantioselective carbocyanation by using carboxylic acid derivatives trimethylsilyl cyanide. Under mild neutral conditions, a diverse range allyl cyanides produced generally good efficiency with high enantioselectivity from bench-stable user-safe chemicals. Moreover, preliminary results also confirm this success can be expanded to 1,3-enynes four-component carbonylative 1,3-enynes.

Язык: Английский

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