分子内受阻路易斯对的官能团化学：路易斯酸位的取代基交换与 9-BBN。

Functional group chemistry at intramolecular frustrated Lewis pairs: substituent exchange at the Lewis acid site with 9-BBN.

机构信息

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

出版信息

Dalton Trans. 2013 Jan 21;42(3):709-18. doi: 10.1039/c2dt31737k.

Abstract

The vicinal frustrated P/B Lewis pair (FLP) Mes(2)PCH(2)CH(2)B(C(6)F(5))(2) reacts with 9-borabicyclo[3.3.1]nonane (9-BBN) by C(6)F(5)vs. H exchange at boron to give the new [B]-H functionalized FLP Mes(2)PCH(2)CH(2)B(H)(C(6)F(5)) (4) and 9-C(6)F(5)-BBN. The latter was characterized as an isonitrile adduct by X-ray diffraction. The new FLP 4 forms an adduct with pyridine and it undergoes clean hydroboration reactions with 1-pentyne or added styrene or dimesitylvinylphosphane. The products formed stable adducts with pyridine; two such examples were also characterized by X-ray crystal structure analysis. A similar alkyl vs. hydrogen exchange was observed upon treatment of an Al/N based Lewis pair, iBu(2)Al-(Me(3)Si)C=C(H)-N(CH(2)CH(2))(2)NMe (14), with 9-BBN.

摘要

毗邻受阻的 P/B 路易斯对（FLP）Mes(2)PCH(2)CH(2)B(C(6)F(5))(2) 通过硼上的 C(6)F(5)对 H 的交换与 9-硼杂双环[3.3.1]壬烷（9-BBN）反应，得到新的 [B]-H 官能化 FLP Mes(2)PCH(2)CH(2)B(H)(C(6)F(5)) (4) 和 9-C(6)F(5)-BBN。后者通过 X 射线衍射被表征为异腈加合物。新的 FLP 4 与吡啶形成加合物，并且它与 1-戊炔或添加的苯乙烯或二甲基乙烯基膦进行干净的硼氢化反应。形成的产物与吡啶形成稳定的加合物；其中两个这样的例子也通过 X 射线晶体结构分析进行了表征。在 Al/N 基路易斯对，iBu(2)Al-(Me(3)Si)C=C(H)-N(CH(2)CH(2))(2)NMe (14) 与 9-BBN 反应时，观察到类似的烷基对氢交换。