Regioselective Synthesis of α,α-Difluorocyclopentanone Derivatives: Domino Nickel-Catalyzed Difluorocyclopropanation/Ring-Expansion Sequence of Silyl Dienol Ethers

被引：28

作者：

Aono, Tatsuya ^{[1
]}

Sasagawa, Hisashi ^{[1
]}

Fuchibe, Kohei ^{[1
]}

Ichikawa, Junji ^{[1
]}

机构：

[1] Univ Tsukuba, Fac Pure & Appl Sci, Div Chem, Tsukuba, Ibaraki 3058571, Japan

来源：

ORGANIC LETTERS | 2015年 / 17卷 / 23期

关键词：

VINYLCYCLOPROPANE REARRANGEMENT; GEM-DIFLUOROCYCLOPROPANES; EFFICIENT SYNTHESIS; DIFLUOROCARBENE; COMPLEXES; CYCLOPROPANATION; GENERATION; KETONES; PHENYL(TRIFLUOROMETHYL)MERCURY; DIFLUOROMETHYLATION;

D O I：

10.1021/acs.orglett.5b02726

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Silyl dienol ethers prepared from alpha,beta-unsaturated ketones underwent nickel-catalyzed difluorocyclopropanation of the electron-rich alkene moiety with trimethylsilyl 2,2-difluoro-2-(fluorosulfonyl)acetate. The subsequent vinylcyclopropane cyclopentene rearrangement afforded silyl 5,5-difluorocyclopent-1-en-1-yl ethers in good yields. The obtained five-membered silyl enol ethers were demonstrated to be versatile intermediates for the synthesis of di- and monofluorinated cyclopentanones and cyclopentenones. A nickel difluorocarbene complex is proposed as a key intermediate in the difluorocyclopropanation.

引用

页码：5736 / 5739

页数：4

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