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Morita–Baylis–Hillman‐Type [3,3]‐Rearrangement: Switching from Z ‐ to E ‐Selective α‐Arylation by New Rearrangement Partners
Author(s) -
Zhang Lei,
Bao Wangzhen,
Liang Yuchen,
Pan Wenjing,
Li Dongyang,
Kong Lichun,
Wang ZhiXiang,
Peng Bo
Publication year - 2021
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.202100497
Subject(s) - cope rearrangement , aryl , chemistry , stereoselectivity , rearrangement reaction , stereochemistry , combinatorial chemistry , medicinal chemistry , organic chemistry , catalysis , alkyl
Abstract α‐aryl α,β‐unsaturated carbonyls represent an important class of derivatizable synthetic intermediates, however, the synthesis of such compounds still remains a challenge. Recently, we showcased a novel Z ‐selective α‐arylation of α,β‐unsaturated nitriles with aryl sulfoxides via [3,3]‐rearrangement involving an Morita–Baylis–Hillman (MBH) process. Herein, we demonstrate the feasibility of reversing the stereoselectivity of such MBH‐type [3,3]‐rearrangement by switching to a new pair of rearrangement partners consisting of aryl iodanes and α,β‐unsaturated oxazolines. As a result, the two protocols complement each other in approaching E ‐ or Z ‐α‐aryl α,β‐unsaturated carbonyl derivatives. Mechanistic studies reveal a possible reaction pathway and provide an explanation for the opposite stereoselectivities.