Premium
Enantioselective Intramolecular [2,3]‐Sigmatropic Rearrangement of Aldehydes via a Sulfonium Enamine Intermediate
Author(s) -
Li Li,
Chen Baoli,
Chen Jiean,
Huang Yong
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.202010234
Subject(s) - enantioselective synthesis , sulfonium , chemistry , sigmatropic reaction , enamine , intramolecular force , organocatalysis , carroll rearrangement , combinatorial chemistry , stereochemistry , organic chemistry , catalysis , salt (chemistry)
The rearrangement of sulfur‐containing aldehydes by using a sulfonium enamine intermediate as a formylcarbene mimetic is reported. This is an enantioselective, organocatalytic [2,3]‐sigmatropic rearrangement enabling chiral cyclic sulfides bearing an α‐quaternary chiral center to be prepared in high optical purity. The enantioselectivity is controlled with a cooperative organocatalyst pair consisting of a chiral amine and a chiral phosphoric acid (CPA). The synthetic versatility of this method is demonstrated by its rapid access to structurally diverse chiral spiro S‐heterocycles.