Premium
Mapping the Mechanism of Nickel‐Ferrophite Catalysed Methylation of Baylis–Hillman‐Derived S N 2′ Electrophiles
Author(s) -
Novak Andrew,
Calhorda Maria José,
Costa Paulo Jorge,
Woodward Simon
Publication year - 2009
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.200801029
Subject(s) - chemistry , electrophile , allylic rearrangement , methylation , enantioselective synthesis , stereochemistry , leaving group , halide , nickel , medicinal chemistry , computational chemistry , catalysis , organic chemistry , biochemistry , gene
Enantioselective Ni‐catalysed methylation of Baylis–Hillman‐derived allylic electrophiles in the presence of ferrophite ligands has been investigated computationally and experimentally. The sense and degree of enantioselectivity attained is independent of both the leaving group and the isomeric structure of the initial allylic halide. DFT studies support the selective formation of a limited number of energetically favoured anti and syn π‐allyl intermediates. The observed regio‐ and enantioselectivity can be rationalised based on the energetics of these structures. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)