High‐Valent Copper Catalysis Enables Regioselective Fluoroarylation of Gem‐Difluorinated Cyclopropanes DOI Creative Commons
Xiuli Wu,

Xiangyu Song,

Ying Xia

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(18)

Published: March 9, 2024

Abstract Transition‐metal (TM) catalyzed reaction of gem ‐difluorinated cyclopropanes ( ‐DFCPs) has drawn much attention recently. The generally occurs via the activation distal C─C bond in ‐DFCPs by a low‐valent TM through oxidative addition, eventually producing mono‐fluoro olefins as coupling products. However, achieving regioselective proximal that overcomes intrinsic reactivity catalysis remains elusive. Here, new mode enabled high‐valent copper catalysis, which allows exclusive congested is presented. achieves fluoroarylation uses NFSI (N‐fluorobenzenesulfonimide) electrophilic fluoro reagent and arenes C─H nucleophiles, enabling synthesis diverse CF 3 ‐containing scaffolds. It proposed species plays an important role possibly σ‐bond metathesis.

Language: Английский

Nickel-Catalyzed Addition of C–C Bonds of Amides to Strained Alkenes: The 1,2-Carboaminocarbonylation Reaction DOI
Yuri Ito,

Syun Nakatani,

Ryota Shiraki

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(2), P. 662 - 666

Published: Jan. 10, 2022

C(aryl)-C(═O) bonds of aryl amides can be activated and added across alkenes with the aid a nickel catalyst. This 1,2-carboaminocarbonylation reaction enables dicarbofunctionalization an atom economy 100%.

Language: Английский

Citations

29
Divergent Rh Catalysis: Asymmetric Dearomatization Versus C–H Activation Initiated by C–C Activation DOI
Xiaotong Li,

Lingfei Hu,

Shuo Ma

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4873 - 4881

Published: March 27, 2023

The divergent catalytic reactions based on C–C activation of benzocyclobutenones have been discovered, consisting a highly enantioselective dearomatic "Cut & Sew" transformation and cascade C–C/C–H activation/annulation process. asymmetric dearomatization was achieved with 2.5 mol % [Rh(HQ)(cod)]BF4 3 (S)-dtbm-Segphos, leading to variety enantioenriched polyfused rings (21 examples, up 99% yield enantiometric excess (ee)). While the tandem yields series amide-linked biaryl tricycles (29 89% yield) through net C1–C2 bond Caryl–H metathesis. A detailed density functional theory (DFT) computation revealed that an amide-directed regioselective Rh complex is realized, in contrast known C1–C8 cleavage. origins were further elucidated.

Language: Английский

Citations

22
Deacylative Thiolation by Redox‐Neutral Aromatization‐Driven C−C Fragmentation of Ketones DOI
Xukai Zhou,

Daniel Pyle,

Zining Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 17, 2023

Herein we report the development of deacylative thiolation diverse methyl ketones. The reaction is redox-neutral, and heavy-metal-free, which provides a new way to introduce thioether groups site-specifically unactivated aliphatic positions. It also features excellent functional group tolerance broad substrate scope, thus allowing late-stage derivatization. process benefits from efficient condensation between activation reagent ketone substrates, triggers aromatization-driven C-C fragmentation rapid radical coupling with thiosulfonates. Experimental computational mechanistic studies suggest involvement chain pathway.

Language: Английский

Citations

19
Photoinduced C−O Bond Formation through C−C Bond Cleavage of Alcohols by Suppressing Alcohol Oxidation DOI
Qiang Wu, Peng Hu

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1595 - 1605

Published: Feb. 3, 2024

Abstract Herein, we present a photoinduced deconstructive alkoxyamination of alkyl alcohols catalyzed by iron salts. This transformation involves the initiation alkoxy radicals through chlorine radical‐induced radical formation, followed β ‐scission and trapping resulting carbon with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO). reaction exhibits broad substrate scope (40 examples), including primary secondary that are prone to oxidation combination TEMPO iron. Mechanistic investigations have revealed enhanced coordination chloride ion center inhibits OH process, thereby enabling tolerance alcohols.

Language: Английский

Citations

6
High‐Valent Copper Catalysis Enables Regioselective Fluoroarylation of Gem‐Difluorinated Cyclopropanes DOI Creative Commons
Xiuli Wu,

Xiangyu Song,

Ying Xia

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(18)

Published: March 9, 2024

Abstract Transition‐metal (TM) catalyzed reaction of gem ‐difluorinated cyclopropanes ( ‐DFCPs) has drawn much attention recently. The generally occurs via the activation distal C─C bond in ‐DFCPs by a low‐valent TM through oxidative addition, eventually producing mono‐fluoro olefins as coupling products. However, achieving regioselective proximal that overcomes intrinsic reactivity catalysis remains elusive. Here, new mode enabled high‐valent copper catalysis, which allows exclusive congested is presented. achieves fluoroarylation uses NFSI (N‐fluorobenzenesulfonimide) electrophilic fluoro reagent and arenes C─H nucleophiles, enabling synthesis diverse CF 3 ‐containing scaffolds. It proposed species plays an important role possibly σ‐bond metathesis.

Language: Английский

Citations

6