Catalytic Asymmetric Homologation of 4-Substituted Cyclohexanones with CF3CHN2: Enantioselective Synthesis of α-Trifluoromethyl Cycloheptanones

被引：151
作者：
Li, Shu-Sen [1 ]
Sun, Shuo [1 ]
Wang, Jianbo [1 ,2 ]
机构：
[1] Peking Univ, Beijing Natl Lab Mol Sci BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
[2] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 06期
关键词：
Asymmetric catalysis; Cycloalkanones; Diazo compounds; Scandium; Trifluoromethylation; ROSKAMP REACTION; RING-EXPANSION; DIAZOESTERS; ALDEHYDES; KETONES; FLUORINE; CONSTRUCTION; GENERATION; INSERTION;
D O I：
10.1002/anie.202115098
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Introduction of the trifluoromethyl group (CF3) into organic molecules in an enantioselective manner has attracted significant attention, but still remains a challenging problem. We herein report a catalytic asymmetric trifluoromethylation of cyclic ketones via a Sc-III/chiral bisoxazoline-catalyzed homologation reaction by employing 2,2,2-trifluorodiazoethane (CF3CHN2) as the CF3 source. This desymmetrization process is highly efficient and generates two chiral centers with excellent diastereoselectivity and enantioselectivity, affording chiral alpha-trifluoromethyl cyclic ketones in a straightforward manner.
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页数：6
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