α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids DOI
Xiang Huang, Dongmei Fang, Xihong Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Language: Английский

Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C–H Alkylation of Allylic Alcohols DOI
Yusuke Kuroda, Takashi Chiba,

Moe Kawajiri

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

We present a protocol for regioselective allylic C-H alkylation of alcohols, consisting sequential azo-ene reaction and attendant Pd-catalyzed substitution with Grignard reagents. Notable features this work include: (1) C(sp3)-C(sp3) bond formation is achieved under Pd-catalysis, (2) the proceeds retention configuration at electrophilic carbon as well olefin geometry.

Language: Английский

Citations

0
α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids DOI
Xiang Huang, Dongmei Fang, Xihong Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Language: Английский

Citations

0