Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
J Am Chem Soc. 2021 Sep 15;143(36):14422-14427. doi: 10.1021/jacs.1c06186. Epub 2021 Sep 7.
Boron-homologation reactions represent an efficient and programmable approach to prepare alkylboronates, which are valuable and versatile synthetic intermediates. The typical boron-homologation reaction, also known as the Matteson reaction, involves formal carbenoid insertions into C-B bonds. Here we report the development of aza-Matteson reactions via carbenoid insertions into the N-B bonds of aminoboranes. By changing the leaving groups of the carbenoids and altering Lewis acid activators, selective mono- and double-methylene insertions can be realized to access various α- and β-boron-substituted tertiary amines, respectively, from common secondary amines. The derivatization of complex amine-containing bioactive molecules, diverse functionalization of the boronate products, and sequential insertions of different carbenoids have also been achieved.
硼同系化反应是一种高效且可编程的方法，可用于制备烷基硼酸酯，后者是具有广泛用途的重要合成中间体。典型的硼同系化反应，也称为 Matteson 反应，涉及卡宾型化合物对 C-B 键的形式插入。在此，我们报告了氮宾型化合物对氨硼烷的 N-B 键的加成反应，发展了aza-Matteson 反应。通过改变卡宾型化合物的离去基团并改变路易斯酸活化剂，可以实现选择性的单-和双亚甲基插入，分别从常见的仲胺中得到各种 α-和 β-硼取代的叔胺。复杂含胺生物活性分子的衍生化、硼酸盐产物的多样化官能化以及不同卡宾型化合物的顺序插入也已实现。
