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Oxidative Allene Amination for the Synthesis of Azetidin‐3‐ones
Author(s) -
Burke Eileen G.,
Schomaker Jennifer M.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504723
Subject(s) - allene , regioselectivity , chemistry , steric effects , amination , silylation , azetidine , axial chirality , electrophile , chirality (physics) , electrophilic amination , combinatorial chemistry , bicyclic molecule , stereochemistry , catalysis , organic chemistry , enantioselective synthesis , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
Regioselectivity in the aziridination of silyl‐substituted homoallenic sulfamates is readily diverted to the distal double bond of the allene to yield endocyclic bicyclic methyleneaziridines with excellent stereocontrol. Subsequent reaction with electrophilic oxygen sources initiates facile rearrangement to densely functionalized, fused azetidin‐3‐ones in excellent d.r., effectively transferring the axial chirality of the allene to central chirality in the products. The steric nature of the silyl group dictates which of the two rings of the fused azetidin‐3‐one will undergo further functionalization, providing an additional element of diversity for the preparation of enantioenriched azetidine scaffolds with potential biological activity.