Expanding the utility of Brønsted base catalysis: Biomimetic enantioselective decarboxylative reactions
Pan, Y. Kee, C.W. Jiang, Z. Ma, T. Zhao, Y. Yang, Y. Xue, H. Tan, C.-H.
Pan, Y.
Kee, C.W.
Jiang, Z.
Ma, T.
Yang, Y.
Xue, H.
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Alternative Title
Abstract
As a result of the low reactivity of simple esters, the use of them as nucleophiles in direct asymmetric transformations is a long-standing challenge in synthetic organic chemistry. Nature approaches this difficulty through a decarboxylative mechanism, which is used for polyketide synthesis. Inspired by nature, we report guanidine-catalyzed biomimetic decarboxylative C-C and C-N bond-formation reactions. These highly enantioselective decarboxylative Mannich and amination reactions utilized malonic acid half thioesters as simple ester surrogates. It is proposed that nucleophilic addition precedes decarboxylation in the mechanism, which has been investigated in detail through the identification of intermediates by using electrospray ionization (ESI) mass-spectrometric analysis and DFT calculations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Keywords
amination, biomimetic synthesis, decarboxylation, density functional calculations, Mannich reaction, organocatalysis
Source Title
Chemistry - A European Journal
Publisher
Series/Report No.
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Date
2011-07-18
DOI
10.1002/chem.201100687
Type
Article