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BIMP-Catalyzed 1,3-Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones.

ABSTRACT: A bifunctional iminophosphorane (BIMP)-catalysed enantioselective synthesis of ?,?-unsaturated cyclohexenones through a facially selective 1,3-prototropic shift of ?,?-unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. ?,?-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.

SUBMITTER: Golec JC

PROVIDER: S-EPMC7540019 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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BIMP-Catalyzed 1,3-Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones.

Golec Jonathan C JC Carter Eve M EM Ward John W JW Whittingham William G WG Simón Luis L Paton Robert S RS Dixon Darren J DJ

Angewandte Chemie (International ed. in English) 20200807 40

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). Compu ...[more]

PMID: 32558981

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