A Perspective on Late-Stage Aromatic C–H Bond Functionalization

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2399 - 2414

Опубликована: Янв. 27, 2022

Late-stage functionalization of C-H bonds (C-H LSF) can provide a straightforward approach to the efficient synthesis functionalized complex molecules. However, LSF is challenging because bond must be in presence various other functional groups. In this Perspective, we evaluate aromatic on basis four criteria─reactivity, chemoselectivity, site-selectivity, and substrate scope─and our own views current challenges as well promising strategies areas growth going forward.

Язык: Английский

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C–H deuteration of organic compounds and potential drug candidates

Chemical Society Reviews, Год журнала: 2022, Номер 51(8), С. 3123 - 3163

Опубликована: Янв. 1, 2022

This review summarises deuteration methods of various organic motifs containing C(sp 2 )−H and 3 bonds utilizing C−H bond functionalisation as a key step along with variety catalysts, exemplifies their biological relevance.

Язык: Английский

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Sustainable Thioetherification via Electron Donor–Acceptor Photoactivation Using Thianthrenium Salts

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(22)

Опубликована: Март 16, 2022

Abstract The synthesis of sulfides has been widely studied because this functional subunit is prevalent in biomolecules and pharmaceuticals, as well being a useful synthetic platform for further elaboration. Thus, various methods to build C−S bonds have developed, but typically they require the use precious metals or harsh conditions. Electron donor–acceptor (EDA) complex photoactivation strategies emerged versatile sustainable ways achieve bond formation, avoiding challenges associated with previous methods. This work describes an open‐to‐air, photoinduced, site‐selective C−H thioetherification from readily available reagents via EDA formation that tolerates wide range different groups. Moreover, C(sp 2 )−halogen remain intact using protocol, allowing late‐stage installation sulfide motif bioactive scaffolds, while yet modification through more traditional C−X cleavage protocols. Additionally, mechanistic investigations support envisioned scenario.

Язык: Английский

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Organothianthrenium salts: synthesis and utilization

Chemical Science, Год журнала: 2022, Номер 13(46), С. 13690 - 13707

Опубликована: Янв. 1, 2022

This review summarizes the synthesis of diverse organothianthrenium salts from various precursors and their applications in organic to forge new C–C, C–H C–heteroatom bonds by C–S bond cleavage with different mechanistic considerations.

Язык: Английский

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Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 13542 - 13548

Опубликована: Июнь 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Язык: Английский

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Cu-Mediated Thianthrenation and Phenoxathiination of Arylborons

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 10431 - 10440

Опубликована: Апрель 26, 2023

Great success in synthetic chemistry is motivated by the development of novel and reactive linchpins for carbon-carbon carbon-heteroatom bond formation reactions, which has dramatically altered chemists' approach to building molecules. Herein, we report ready synthesis aryl sulfonium salts, a versatile electrophilic linchpin, via Cu-mediated thianthrenation phenoxathiination commercially available arylborons with thianthrene phenoxathiine, providing series salts high efficiency. More importantly, leveraging sequential Ir-catalyzed C-H borylation arylborons, formal arenes also achieved. The undirected normally occurred at less steric hindrance position, thus complementary method comparison thianthrenation. This process capable late-stage functionalization pharmaceuticals, might find wide applications both industry academic sectors.

Язык: Английский

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A Practical and Regioselective Strategy for Aromatic C–H Difunctionalization via Site-Selective C–H Thianthrenation

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1813 - 1818

Опубликована: Фев. 22, 2024

Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C–H difunctionalization of compounds without directing groups or known initiating reagent. A series functionalized syntheses bioactive molecules further demonstrated potential this strategy.

Язык: Английский

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Standardized Approach for Diversification of Complex Small Molecules via Aryl Thianthrenium Salts

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 21, 2025

Thianthrenation is a useful strategy for the late-stage diversification of complex small molecules owing to positional selectivity and synthetic versatility thianthrenium salts as electrophilic linchpins. However, substrate-dependent identification suitable reaction conditions thianthrenation can be difficult. Reported functionalization vary significantly and, in some instances, lack robustness practicality. Herein, we report generalized approach preparation two manifolds practical, robust, parallel salts.

Язык: Английский

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Thianthrenium-enabled sulfonylation via electron donor-acceptor complex photoactivation

Chem Catalysis, Год журнала: 2022, Номер 2(4), С. 898 - 907

Опубликована: Апрель 1, 2022

Sulfone-containing compounds are prevalent building blocks in pharmaceutical agents and other biomolecules, they serve as key intermediates the synthesis of complex scaffolds. During past decade, several methods have been developed to access sulfones. These strategies, however, require use strong reaction conditions, limiting their substrate scope. Recently, visible-light-mediated transformations emerged novel platforms unprecedented structural motifs. This report demonstrates thianthrenium-enabled sulfonylation via intra-complex charge transfer generate transient aryl- persistent sulfonyl radicals that undergo selective coupling alkyl- (hetero)aryl sulfones under ambient conditions. strategy allows retention halide handles, presenting a complementary approach transition metal-mediated photoredox couplings. Furthermore, this high functional group tolerance is amenable late-stage functionalization biomolecules. Mechanistic investigations support intermediacy electron donor-acceptor (EDA) complexes.

Язык: Английский

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Photoredox-Catalyzed α-Sulfonylation of Ketones from Sulfur Dioxide and Thianthrenium Salts

Organic Letters, Год журнала: 2022, Номер 24(15), С. 2955 - 2960

Опубликована: Апрель 13, 2022

A photoredox-catalyzed sulfonylation of silyl enol ethers with DABCO·(SO2)2 and thianthrenium salts is achieved, providing diverse β-keto sulfones in moderate to good yields. This protocol features easily accessible starting materials functional group compatibility, enabling the introduction various functionalized sulfonyl groups into ketones. Furthermore, as one important industrial raw materials, methanol can be employed methyl source prepare α-methylsulfonated ketones through a intermediate for first time.

Язык: Английский

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