Metal-free photocatalytic cross-electrophile coupling enables C1 homologation and alkylation of carboxylic acids with aldehydes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 19, 2024

In contemporary drug discovery, enhancing the sp

Language: Английский

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Enantioselective alkylation of α-amino C(sp3)−H bonds via photoredox and nickel catalysis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(8), P. 889 - 899

Published: July 4, 2024

Language: Английский

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Utilization of C(sp³)‐Carboxylic Acids and Their Redox‐Active Esters in Decarboxylative Carbon−Carbon Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(15), P. 3693 - 3736

Published: May 11, 2021

Abstract Over the last several years, radical‐mediated decarboxylative cross‐coupling reactions employing alkyl carboxylic acids have emerged as a powerful tool for regiospecific construction of carbon−carbon bonds. Under thermal or photocatalytic conditions, wide variety C( sp 3 )‐carboxylic and their redox‐active esters undergo C−C bond formation with suitable reactant partners, leading to complex chemical scaffolds wide‐ranging applications. This synthetic strategy has advantages over more conventional organometallic reagents, including abundant starting material availability high functional group tolerance associated mild reaction conditions. review article highlights recent developments in functionalization α‐heteroatom‐substituted well challenging unactivated acids, representative examples discussed against backdrop insightful comments on mechanisms. In addition, synthesis natural products, drug molecules, late‐stage modification bioactive molecules this non‐traditional are included. been categorized into three main sections that organized around type being forged: )−C( 2 ), ). Further, separately each section. magnified image

Language: Английский

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Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(11), P. 2678 - 2722

Published: March 31, 2021

Abstract Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic derivatives in decarboxylative couplings has proven be a valuable tool for construction C−C C‐heteroatom bonds. This synthetic strategy provides complementary bond disconnection traditional cross‐coupling methods. In this review, we provide comprehensive overview decarboxylation‐initiated intermolecular formation, outlining several main mechanistic concepts combined with early examples highlighting achievements made past decade until January 2021. these reactions, undergo initial decarboxylation then react other heteroatom electrophiles nucleophiles, thus replacing carboxylate group prevalent functionality. magnified image

Language: Английский

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Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(6), P. 730 - 746

Published: Dec. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Language: Английский

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Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Language: Английский

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Metal-Free Photosynthesis of Alkylated Benzimidazo[2,1-a]isoquinoline-6(5H)-ones and Indolo[2,1-a]isoquinolin-6(5H)-ones in PEG-200

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(13), P. 9055 - 9066

Published: June 23, 2021

A visible-light-induced decarboxylation reaction was developed for the synthesis of alkylated benzimidazo[2,1-a]isoquinoline-6(5H)-ones and indolo[2,1-a]isoquinolin-6(5H)-ones under metal-free conditions. Impressively, metal catalysts traditionally volatile organic solvents could be effectively avoided.

Language: Английский

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Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp³)–H Bonds and Aliphatic Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(36), P. 14667 - 14675

Published: Aug. 31, 2021

Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these either work only activated or bring in a narrow set functional groups. Here we describe Cu-catalyzed process diverse both unactivated acids. The is enabled by trapping alkyl radicals generated through abstraction arylsulfonyl-based SOMO-philes, which introduces large array C, N, S, Se, halide-based chemoselectivity can be switched C-H to decarboxylative matching bond dissociation energy reagent with that target O-H bond.

Language: Английский

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Regioselective Access to Vicinal Diamines by Metal‐Free Photosensitized Amidylimination of Alkenes with Oxime Esters

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 9, 2022

A metal-free photosensitized protocol for regioselective diamination of alkene feedstocks over a single step was developed based on the rationally designed bifunctional reagent, thus affording range differentially protected 1,2-diamines in moderate to high yields. Mechanistic studies reveal that reaction is initiated with triplet-triplet energy transfer between thioxanthone catalyst and followed by fragmentation simultaneously generate long-lived iminyl radical transient amidyl radical. The excellent regioselectivity presumably stems from large reactivity difference two different N-centered species. This characterized regioselectivity, broad functional group tolerance, mild conditions, which would enrich diversity versatility facilitate diversity-oriented synthesis 1,2-diamine-containing complex molecule scaffolds.

Language: Английский

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Exploiting photoredox catalysis for carbohydrate modification through C–H and C–C bond activation

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(11), P. 782 - 805

Published: Sept. 21, 2022

Language: Английский

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