Mapping the Mechanism of Nickel-Ferrophite Catalysed Methylation of Baylis-Hillman-Derived S(N)2 ' Electrophiles

resumo

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 pi-allyl. intermediates. The observed regio- and enantioselectivity can be rationalised based on the energetics of these structures. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

palavras-chave

DENSITY; COMPLEXES; ALLYL

categoria

Chemistry

autores

Novak, A; Calhorda, MJ; Costa, PJ; Woodward, S

nossos autores

Grupos

agradecimentos

Financial support from European Union (project FP6-NMP3-C-2003-505267 associated with Ligbank (R) and the COST D40 programme) is acknowledged. One of us (A. N.) is grateful to GlaxoSmithKline for the provision of a studentship. M. J. C. and P. J. C. thank Fundacao do Ministerio de Ciencia e Tecnologia (FCT), Programa Operacional Ciencia e Inovacao (POCI) and Fundo Europeu de Desenvolvimento Regional (project POCI/QUI/58925/2004).

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