Highly Enantioselective, Intermolecular Hydroamination of Allenyl Esters Catalyzed by Bifunctional Phosphinothioureas
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Date
2014
Author(s)
Fang, Yuan-Qing
Tadross, Pamela
M.
Publisher
American Chemical
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Citation
Fang, Yuan-Qing, Pamela M. Tadross, and Eric N. Jacobsen. 2014. “Highly Enantioselective, Intermolecular Hydroamination of Allenyl Esters Catalyzed by Bifunctional Phosphinothioureas.” Journal of the American Chemical Society 136 (52): 17966-17968. doi:10.1021/ja5117638. http://dx.doi.org/10.1021/ja5117638.
Abstract
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 conjugate addition of a thiourea-bound carbamate anion to a vinyl phosphonium ion resulting from covalent activation of the allenyl ester substrate.
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