Premium
Diastereoselective Aza‐Mislow–Evans Rearrangement of N ‐Acyl tert ‐Butanesulfinamides into α‐Sulfenyloxy Carboxamides
Author(s) -
Tang Fan,
Yao Yun,
Xu YanJun,
Lu ChongDao
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.201809551
Subject(s) - stereocenter , ketene , chemistry , chirality (physics) , keto–enol tautomerism , silylation , enol , carbon atom , stereochemistry , medicinal chemistry , enantioselective synthesis , catalysis , organic chemistry , tautomer , ring (chemistry) , chiral symmetry breaking , physics , quantum mechanics , quark , nambu–jona lasinio model
A diastereoselective [2,3] rearrangement of O ‐silyl N ‐sulfinyl N,O‐ketene acetals derived from chiral N ‐acyl tert ‐butanesulfinamides was developed, giving α‐sulfenyloxy carboxamides with excellent enantioselectivity. Enolization and subsequent silylation of N ‐acyl tert ‐butanesulfinamides initiate this aza variant of the Mislow–Evans rearrangement, in which the chirality at the sulfur atom in the rearrangement precursors is faithfully transferred to the α‐carbon stereocenter of the products. The Ellman sulfinamide, often used as a chiral ammonia equivalent, can serve in this rearrangement as a chiral precursor for the asymmetric synthesis of α‐oxygen‐functionalized carboxamides.