BIMP-Catalyzed 1,3-Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones |
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| Authors: | Jonathan C. Golec Eve M. Carter John W. Ward William G. Whittingham Luis Simón Robert S. Paton Darren J. Dixon |
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| Affiliation: | 1. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA UK;2. Leverhulme Research Centre for Functional Materials Design, The Materials Innovation Factory, Department of Chemistry, University of Liverpool, Liverpool, L7 3NY UK;3. Jealott's Hill International Research Centre, Bracknell, Berkshire, RG42 6EY UK;4. Facultad de Ciencias Químicas, Universidad de Salamanca, Plaza de los Caídos 1–5, 37008 Salamanca, Spain;5. Department of Chemistry, Colorado State University, 1301 Center Ave, Ft. Collins, CO, 80523-1872 USA |
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| Abstract: | A bifunctional iminophosphorane (BIMP)-catalysed enantioselective synthesis of α,β-unsaturated cyclohexenones through a facially selective 1,3-prototropic shift of β,γ-unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β-Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings. |
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| Keywords: | bifunctional iminophosphoranes chiral cyclohexenone asymmetric catalysis organocatalysis prototropic shift |
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