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Enantioselective Catalytic Aldehyde α‐Alkylation/Semipinacol Rearrangement: Construction of α‐Quaternary‐δ‐Carbonyl Cycloketones and Total Synthesis of (+)‐Cerapicol
Author(s) -
Yang Jie,
Zhang XiaoMing,
Zhang FuMin,
Wang ShaoHua,
Tu YongQiang,
Li Zhen,
Wang XiChao,
Wang Hong
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202001100
Subject(s) - enantioselective synthesis , aldehyde , electrophile , chemistry , alkylation , enamine , allylic rearrangement , total synthesis , tsuji–trost reaction , intramolecular force , catalysis , ketone , organocatalysis , organic chemistry , combinatorial chemistry
An enantioselective aldehyde α ‐alkylation/semipinacol rearrangement was achieved through organo‐SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring‐expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α ‐quaternary‐ δ ‐carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)‐cerapicol.