Department of Chemistry, Dalhousie University , 6274 Coburg Road, P.O. Box 15000, Halifax, Nova Scotia, Canada B3H 4R2.
X-ray Crystallography Laboratory, Department of Chemistry, University of Alberta , Edmonton, Alberta, Canada T6G 2G2.
Org Lett. 2017 Oct 20;19(20):5565-5568. doi: 10.1021/acs.orglett.7b02695. Epub 2017 Oct 10.
The synthesis and study of the catalytic activity of 1,2,4,3-triazaphospholenes (TAPs) is reported. TAPs represent a more modular scaffold than previously reported diazaphospholenes. TAP halides were shown to catalyze the 1,2 hydroboration of 19 imines, and three α,β unsaturated aldehydes with pinacolborane, including examples that did not undergo hydroboration by previously reported diazaphospholene systems. DFT calculations support a mechanism where a triazaphospholene cation interacts with the substrate, a mechanism distinct from diazaphospholene catalyzed hydroborations.
报道了 1,2,4,3-三氮杂磷环（TAPs）的合成和催化活性研究。TAPs 代表了比以前报道的二氮杂磷环更具模块性的支架。TAP 卤化物被证明可以催化 pinacolborane 对 19 个亚胺和三个α,β不饱和醛的 1,2 氢硼化反应，包括一些以前报道的二氮杂磷环体系不能进行氢硼化的例子。DFT 计算支持一种机制，其中三氮杂磷环阳离子与底物相互作用，这种机制与二氮杂磷环催化的氢硼化反应不同。
