Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis–Hillman-Derived SN2′ Electrophiles

✍ Scribed by Andrew Novak; Maria José Calhorda; Paulo Jorge Costa; Simon Woodward

• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 390 KB
• Volume: 2009
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200801029

✦ Synopsis

Abstract

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)