Premium
Interrupted Baeyer–Villiger Rearrangement: Building A Stereoelectronic Trap for the Criegee Intermediate
Author(s) -
Vil' Vera A.,
dos Passos Gomes Gabriel,
Bityukov Oleg V.,
Lyssenko Konstantin A.,
Nikishin Gennady I.,
Alabugin Igor V.,
Terent'ev Alexander O.
Publication year - 2018
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.201712651
Subject(s) - chemistry , ring (chemistry) , alkyl , medicinal chemistry , rearrangement reaction , cope rearrangement , stereochemistry , photochemistry , computational chemistry , organic chemistry , catalysis
The instability of hydroxy peroxyesters, the elusive Criegee intermediates of the Baeyer–Villiger rearrangement, can be alleviated by selective deactivation of the stereoelectronic effects that promote the 1,2‐alkyl shift. Stable cyclic Criegee intermediates constrained within a five‐membered ring can be prepared by mild reduction of the respective hydroperoxy peroxyesters (β‐hydroperoxy‐β‐peroxylactones) which were formed in high yields in reaction of β‐ketoesters with BF 3 ⋅Et 2 O/H 2 O 2 .