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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Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 2313 - 2382

Published: Jan. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Language: Английский

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A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5659 - 5666

Published: Jan. 1, 2022

General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation aryl radicals for C–H functionalization arenes.

Language: Английский

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Copper-photocatalyzed ATRA reactions: concepts, applications, and opportunities

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(13), P. 5287 - 5299

Published: Jan. 1, 2022

This review summarizes the different applications and underlying concepts that are applied for Cu( i )- or ii )-photocatalyzed difunctionalizations of alkenes.

Language: Английский

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Enantioselective Radical Trifluoromethylation of Benzylic C–H Bonds via Cooperative Photoredox and Copper Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(30), P. 13468 - 13474

Published: July 21, 2022

The first enantioselective radical trifluoromethylation of benzylic C–H bonds has been established by a cooperative photoredox and copper catalysis system, providing straightforward access to structurally diverse products in good yields with excellent enantioselectivities under mild conditions. Our method features broad substrate scope functional group compatibility. Merging the is essential for reaction, where used generation radicals from alkyl arenes through hydrogen atom transfer process radicals.

Language: Английский

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Radical transformations for allene synthesis

Chemical Science, Journal Year: 2022, Volume and Issue: 13(29), P. 8491 - 8506

Published: Jan. 1, 2022

Allenes are valuable organic molecules that feature unique physical and chemical properties. They not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such pharmaceuticals, functional materials. Therefore, many remarkable elegant methodologies have been established synthesis allenes. Recently, more methods radical allenes developed, clearly emphasizing associated great synthetic values. In this perspective, we will discuss recent important advances

Language: Английский

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Catalytic Asymmetric Construction of Axially and Centrally Chiral Heterobiaryls by Minisci Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(13), P. 6040 - 6049

Published: March 24, 2022

Axially chiral biaryls and heterobiaryls constitute the most represented subclass of atropisomers with prevalence in natural products, bioactive compounds, privileged ligand/catalysts, optically pure materials. Despite many ionic protocols for their construction, radical-based variants represent another highly desirable intriguing strategy but are far less developed. Moreover, efficient synthesis axially heterobiaryl molecules, especially ones having multiple heteroatoms other types elements, through radical routes remains extremely limited. We herein disclose first catalytic asymmetric, metal-free construction centrally by Minisci reaction 5-arylpyrimidines α-amino acid-derived redox-active esters. This is enabled use 4CzIPN as an organic photoredox catalyst conjunction a phosphoric acid catalyst. The achieved variety interesting featuring union α-branched amine generally excellent regio-, diastereo-, enantioselectivity (up to 82% yield; >19:1 dr; >99% ee). finding also builds up new platform development desymmetrization methods via radical-involved atroposelective functionalization at heteroarene prochiral heterobiaryls.

Language: Английский

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Photoinduced copper-catalyzed enantioselective coupling reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(7), P. 2358 - 2376

Published: Jan. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Language: Английский

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Site- and enantioselective allylic and propargylic C–H oxidation enabled by copper-based biomimetic catalysis

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Language: Английский

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Enantioselective Radical Addition to Ketones through Lewis Acid-Enabled Photoredox Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 22140 - 22149

Published: Nov. 22, 2022

Photocatalysis opens up a new window for carbonyl chemistry. Despite multitude of photochemical reactions compounds, visible light-induced catalytic asymmetric transformations remain elusive and pose formidable challenge. Accordingly, the development simple, efficient, economic systems is ideal pursuit chemists. Herein, we report an enantioselective radical photoaddition to ketones through Lewis acid-enabled photoredox catalysis wherein in situ formed chiral N,N'-dioxide/Sc(III)-ketone complex serves as temporary photocatalyst trigger single-electron transfer oxidation silanes generation nucleophilic species, including primary, secondary, tertiary alkyl radicals, giving various enantioenriched aza-heterocycle-based alcohols good excellent yields enantioselectivities. The results electron paramagnetic resonance (EPR) high-resolution mass spectrum (HRMS) measurements provided favorable evidence stereocontrolled addition process involved this reaction.

Language: Английский

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