Open AccessSynthesis of Highly Congested Tertiary Alcohols via the [3,3] Radical Deconstruction of Breslow Intermediates
Author(s) -
Roger Machín Rivera,
Nikolas Burton,
Luke D. Call,
Marshall A. Tomat,
Vincent N. G. Lindsay
Publication year - 2022
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.2c01627
Subject(s) - chemistry , pericyclic reaction , sigmatropic reaction , benzaldehyde , tertiary alcohols , cope rearrangement , alkene , organic synthesis , alcohol , organic chemistry , catalysis
Pericyclic processes such as [3,3]-sigmatropic rearrangements leading to the rapid generation of molecular complexity constitute highly valuable tools in organic synthesis. Herein, we report the formation of particularly hindered tertiary alcohols via rearrangement of Breslow intermediates formed in situ from readily available N -allyl thiazolium salts and benzaldehyde derivatives. Experimental mechanistic studies performed suggest that the reaction proceeds via a close radical pair which recombine in a regio- and diastereoselective manner, formally leading to [3,3]-rearranged products.