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Rearrangement Reactions Leading to Optically Active α,α‐Disubstituted Primary Allylamines
Author(s) -
Hennum Martin,
Odden Hege Hortemo,
Gundersen LiseLotte
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201601446
Subject(s) - allylic rearrangement , chemistry , cyanate , isocyanate , oxazoline , enantioselective synthesis , double bond , chirality (physics) , optically active , rearrangement reaction , diene , organic chemistry , catalysis , chiral symmetry breaking , physics , natural rubber , quantum mechanics , nambu–jona lasinio model , polyurethane , quark
Synthetic routes to α,α‐disubstituted allylamines have been examined. Racemic compounds were conveniently prepared by thermal Overman rearrangements of primary allylic alcohols with trisubstituted double bonds, but rearrangement of these substrates using the only commercially available compound known to catalyze enantioselective Overman rearrangements, the cobalt oxazoline palladacycle ( R )‐COP‐Cl, failed. Instead, optically active secondary allylic alcohols with trisubstituted double bonds, obtained by Corey–Bakshi–Shibata reduction of the corresponding methyl ketones, were synthesized and converted into α,α‐disubstituted allylamines through a thermal Overman rearrangement or an allylic‐cyanate‐to‐isocyanate rearrangement. High chirality transfer (90–99 %) was obtained for both reaction sequences, but the yields were greatly improved when the allylic‐cyanate‐to‐isocyanate rearrangement was used.