期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 17, 期 30, 页码 8363-8370出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201100687
关键词
amination; biomimetic synthesis; decarboxylation; density functional calculations; Mannich reaction; organocatalysis
资金
- National University of Singapore
- [R-143-000-337-112]
- [R-143-000-376-112]
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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据