Škoch Karel, Daniliuc Constantin G, Kehr Gerald, Erker Gerhard
Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6757-6763. doi: 10.1002/anie.202014562. Epub 2021 Feb 1.
The Mes P-C≡C-SiMe alkyne reacts with the borane H B-Fmes by means of a rare 1,1-hydroboration reaction to give an unsaturated C -bridged frustrated P/B-H Lewis pair. Most of its reactions are determined by the presence of the B-H functionality at the FLP function and the activated connecting carbon-carbon double bond. It reduces carbon monoxide to the formyl stage. With nitriles it reacts in an extraordinary way: it undergoes a reaction sequence that eventually results in the formation of a P-substituted dihydro-1,2-azaborole derivative. Several similar examples were found. In one case a P-ylide was isolated that was related to an intermediate of the reaction sequence. It subsequently opened in an alternative way to give an alkenyl borane product.
Mes P-C≡C-SiMe炔烃通过罕见的1,1-硼氢化反应与硼烷H B-Fmes反应，生成不饱和C桥连的受阻P/B-H路易斯对。其大多数反应由FLP功能处的B-H官能团和活化的连接碳-碳双键的存在决定。它将一氧化碳还原到甲酰基阶段。与腈反应时，它以一种特殊的方式进行：它经历一系列反应，最终形成P取代的二氢-1,2-氮杂硼烷衍生物。发现了几个类似的例子。在一个案例中，分离出了一种与反应序列中间体相关的磷叶立德。它随后以另一种方式开环，得到烯基硼烷产物。
