Premium
Direct Noncovalent Activation of α,β‐Unsaturated Aldehydes for the Stereodivergent Synthesis of Substituted Cyclohexenes
Author(s) -
Xie JiKang,
Wang Yang,
Lin JunBing,
Ren XiaoRui,
Xu PengFei
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701315
Subject(s) - stereocenter , bifunctional , steric effects , catalysis , chemistry , enantiomer , non covalent interactions , aryl , combinatorial chemistry , enantioselective synthesis , stereochemistry , organocatalysis , molecule , organic chemistry , alkyl , hydrogen bond
Abstract HOMO‐raising noncovalent activation of α‐aryl α,β‐unsaturated aldehydes using a bifunctional Brønsted base catalyst is achieved. The catalytically generated dienolate intermediate undergoes all‐carbon [4+2] cyclizations with nitroolefins, leading to chiral cyclohexenes with four contiguous stereocenters in high yields and with excellent enantioseletivity. Furthermore, the diastereodivergent synthesis of the products is realized by introducing a second steric control to the bifunctional catalyst; 4 isomers out of 16 possible stereoisomers of the products were selectively produced by simple use of two catalysts and their (pseudo)enantiomers. The results presented here provide new insights into the remote activation of the carbonyl functionality as well as the stereodivergent synthesis of complex chiral molecules with multiple stereocenters.