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Asymmetric and Geometry‐Selective α‐Alkenylation of α‐Amino Acids
Author(s) -
Abas Hossay,
MasRoselló Josep,
Amer Mostafa Mahmoud,
Durand Derek J.,
Groleau Robin R.,
Fey Natalie,
Clayden Jonathan
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201813984
Subject(s) - enantiopure drug , intramolecular force , chemistry , amino acid , hydrolysis , double bond , molecular geometry , stereochemistry , absolute configuration , enantioselective synthesis , organic chemistry , molecule , catalysis , biochemistry
Both E ‐ and Z ‐ N ′‐alkenyl urea derivatives of imidazolidinones may be formed selectively from enantiopure α‐amino acids. Generation of their enolate derivatives in the presence of K + and [18]crown‐6 induces intramolecular migration of the alkenyl group from N′ to Cα with retention of double bond geometry. DFT calculations indicate a partially concerted substitution mechanism. Hydrolysis of the enantiopure products under acid conditions reveals quaternary α‐alkenyl amino acids with stereodivergent control of both absolute configuration and double bond geometry.