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Highly enantioselective, intermolecular hydroamination of allenyl esters catalyzed by bifunctional phosphinothioureas.

ABSTRACT: Bifunctional phosphinothiourea catalysts have been developed successfully for the highly regio- and enantioselective ?-hydroamination of allenyl and propargyl esters with N-methoxy carbamate nucleophiles to yield ?,?-unsaturated ?-amino acid ester products. In the case of propargyl ester substrates, the reaction proceeds through reversible phosphinothiourea-catalyzed isomerization to the corresponding allenyl ester. The high enantioselectivity of the process is attributed to a cooperative conjugate addition of a thiourea-bound carbamate anion to a vinyl phosphonium ion resulting from covalent activation of the allenyl ester substrate.

SUBMITTER: Fang YQ

PROVIDER: S-EPMC4291748 | biostudies-literature | 2014 Dec

REPOSITORIES: biostudies-literature

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Highly enantioselective, intermolecular hydroamination of allenyl esters catalyzed by bifunctional phosphinothioureas.

Fang Yuan-Qing YQ Tadross Pamela M PM Jacobsen Eric N EN

Journal of the American Chemical Society 20141217 52

Bifunctional phosphinothiourea catalysts have been developed successfully for the highly regio- and enantioselective γ-hydroamination of allenyl and propargyl esters with N-methoxy carbamate nucleophiles to yield α,β-unsaturated γ-amino acid ester products. In the case of propargyl ester substrates, the reaction proceeds through reversible phosphinothiourea-catalyzed isomerization to the corresponding allenyl ester. The high enantioselectivity of the process is attributed to a cooperative conjug ...[more]

PMID: 25496451

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