Expanding the Utility of Brønsted Base Catalysis:
- TCHLab
- Jun 15, 2011
- 1 min read
Biomimetic Enantioselective Decarboxylative Reactions
Yuanhang Pan, Choon Wee Kee, Prof. Zhiyong Jiang, Ting Ma, Yujun Zhao, Yuanyong Yang, Hansong Xue and Prof. Choon‐Hong Tan
Chemistry - An European Journal, 2011, 17, 8363–8370.
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.
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