Making Full Use of TMSCF₃: Deoxygenative Trifluoromethylation/Silylation of Amides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19286 - 19294

Published: July 3, 2024

As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF3) has been widely used for synthesis fluorine-containing molecules. However, to best our knowledge, simultaneous incorporation both TMS- and CF3- groups this reagent onto same carbon products not realized. Herein, we report an unprecedented SmI2/Sm promoted deoxygenative difunctionalization amides with TMSCF3, in which silyl trifluoromethyl are incorporated into final product, yielding α-silyl-α-trifluoromethyl amines high efficiency. Notably, group could be further transformed other functional groups, providing a new method α-quaternary α-CF3-amines.

Language: Английский

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Recent Advances in C—F Bond Formation from Carbon‐Centered Radicals

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(9), P. 1009 - 1031

Published: Dec. 8, 2023

Comprehensive Summary Construction of C—F bonds is a direct and efficient method for introducing fluorine into pharmaceuticals, agrochemicals, materials. Strategies such as nucleophilic, electrophilic, radical, transition‐metal catalyzed fluorination have been developed to meet the demand diverse bond formation. Among them, radical has witnessed with substantial advancement in recent decade. Herein, we reviewed methods formation carbon‐centered radicals key intermediates, especially five years. We introduce paper different fluorinating reagents, strategies generation, application late‐stage functionalization synthesis PET tracers. also indicate current limitations propose direction field future development. Key Scientists Radical was recognized an old uncontrolled reaction that may date back time when element first mixed organic compounds by Henri Moissan 1891. The development slow combination discovery new reagents. Substantial changes took place 2012, example carbon robust mild NFSI Selectfluor, reported Sammis group. In same year, Groves, Lectka, Li, Boger led pioneering works on aliphatic C—H fluorination, decarboxylative fluorofunctionalization alkenes manner. Photoredox catalysis introduced 2013 Chen group, which opens up avenue fluorinative transformations. Most previous focus form C(sp 3 )–F bonds. 2018, challenging non‐directed aromatic solved Ritter coworkers. Direct arene fluoride ion later disclosed Nicewicz group 2019. There are many other scientists made tremendous contribution too limited space list them all. only those discoveries point fluorination.

Language: Английский

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Decarboxylative Nucleophilic Fluorination of Aliphatic Carboxylic Acids

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4257 - 4261

Published: May 13, 2024

Herein, we present a decarboxylative nucleophilic fluorination of carboxylic acids with silver catalyst. This strategy enables the synthesis myriad diverse and valuable fluorinated motifs under mild conditions, demonstrating good functional-group tolerance utility in late-stage functionalization. In contrast to traditional electrophilic fluorination, this method utilizes more readily available fluorinating reagent, providing substantial advantages terms cost efficiency, broad substrate scope, compatibility.

Language: Английский

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Internal 2D networking of silver bromide with bidentate N-heterocyclic carbene ligand enables the formation of inherently heterogeneous reusable catalyst for multicomponent A3 coupling

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(28), P. 12800 - 12806

Published: Jan. 1, 2024

We report the synthesis of an internal 2D networking heterogeneous silver catalyst stabilized by bidentate N-heterocyclic carbene ligands. The Ag–NHC is employed in A 3 coupling reactions and demonstrated reusability for six cycles.

Language: Английский

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Trifluoromethylation Strategies of Alcohols and Phenols

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(11)

Published: July 16, 2024

Abstract In this review, we present a comprehensive update on the latest trifluoromethylation protocols for alcohols, highlighting significant advancements and innovative strategies in rapidly evolving field. Given prevalence of hydroxyl groups pharmaceutical compounds, there is heightened interest synthesizing functionalized organic molecules through −CF 3 functionalization parent alcohols. Recent developments have introduced intriguing methods such as O ‐trifluoromethylation, dehydroxylative trifluoromethoxylation, deoxytrifluoromethylation, oxytrifluoromethylation readily available These enable efficient single‐step construction diverse structures featuring C−CF C−OCF bonds. This review aims to encapsulate progress, structural diversity, mechanistic insights these transformative reactions, emphasizing their substrate scope underlying reaction pathways that drive advancements.

Language: Английский

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