期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 4, 页码 1121-1126出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201102209
关键词
boron; DFT; organocatalysis; reaction mechanisms; synthetic methods
资金
- MICINN [CTQ2010-16226/BQU, CTQ2008-06549-CO2-02/BQU, CSD2006-0003]
- AGAUR [2009SGR-00462, 2009SGR-00116]
- Generalitat Catalunya
- ICIQ Foundation
Bases play an important role in organocatalytic boron conjugate addition reactions. The sole use of MeOH and a base can efficiently transform acyclic and cyclic activated olefins into the corresponding beta-borated products in the presence of diboron reagents. Inorganic and organic bases deprotonate MeOH in the presence of diboron reagents. It is concluded, on the basis of theoretical calculations, NMR spectroscopic data, and ESI-MS experiments, that the methoxide anion forms a Lewis acidbase adduct with the diboron reagent. The sp2 B atom of the methoxidediboron adduct gains a strongly nucleophilic character, and attacks the electron-deficient olefin. The methanol protonates the intermediate, generating the product and another methoxide anion. This appears to be the simplest method to activate diboron reagents and make them suitable for incorporation into target organic molecules.
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