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通过硼烷路易斯酸诱导的环丙基重排形成偕二硼烷及其与二氧化碳的受阻路易斯对反应。

Geminal bis-borane formation by borane Lewis acid induced cyclopropyl rearrangement and its frustrated Lewis pair reaction with carbon dioxide.

作者信息

Liu Yun-Lin, Kehr Gerald, Daniliuc Constantin G, Erker Gerhard

机构信息

Organisch-Chemisches Institut , Universität Münster , Corrensstraße 40 , 48149 Münster , Germany . Email:

出版信息

Chem Sci. 2017 Feb 1;8(2):1097-1104. doi: 10.1039/c6sc03468c. Epub 2016 Sep 16.

DOI:10.1039/c6sc03468c
PMID:28451249
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5369401/
Abstract

Cyclopropylacetylene reacts with two molar equivalents of Piers' borane [HB(CF)] under mild conditions by an addition/rearrangement sequence with cyclopropyl ring opening to give a mixture of two α-B(CF) substituted tetrahydroboroles. This compound forms an active frustrated Lewis pair with P Bu that heterolytically splits dihydrogen and adds carbon dioxide as a geminal chelate bis-boryl component. The respective reactions of the two-fold HB(CF) addition to Ph-CHCHC[triple bond, length as m-dash]CH were studied as a geminal Lewis acid reference. Most of the products were characterized by X-ray diffraction.

摘要

环丙基乙炔在温和条件下与两摩尔当量的皮尔斯硼烷[HB(CF)]通过加成/重排序列反应，环丙基开环，得到两种α-B(CF)取代的四氢硼烷的混合物。该化合物与P Bu形成活性受阻路易斯对，能使氢气异裂分解，并将二氧化碳作为偕二螯合双硼基组分加成。研究了两倍量的HB(CF)加成到Ph-CHCHC≡CH上的相应反应，作为偕二路易斯酸参考。大多数产物通过X射线衍射进行了表征。

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