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Direct Catalytic Enantio- and Diastereoselective Mannich Reaction of Isocyanoacetates and Ketimines

Authors

  • Dr. Irene Ortín,

    1. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK)
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  • Prof. Dr. Darren J. Dixon

    Corresponding author
    1. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK)
    • Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA (UK)===

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  • We thank the EPSRC (Leadership Fellowship to D.J.D.) and the EC [IEF to I.O. (PIEF-GA-2010-275788)] for funding, Alison Hawkins and David Barber of the Department of Chemistry, University of Oxford, for X-ray analysis, and the Oxford Chemical Crystallography Service for the use of their instrumentation.

Abstract

A catalytic asymmetric synthesis of imidazolines with a fully substituted β-carbon atom by a Mannich-type addition/cyclization reaction of isocyanoacetate pronucleophiles and N-diphenylphosphinoyl ketimines has been developed. When a combination of a cinchona-derived aminophosphine precatalyst and silver oxide was employed as a binary catalyst system, good reactivity, high diastereoselectivities (up to 99:1 d.r.), and excellent enantioselectivities (up to 99 % ee) were obtained for a range of substrates.

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