Ye Jian-Heng, Quach Linda, Paulisch Tiffany, Glorius Frank
Organisch-Chemisches Institut , Westfälische Wilhelms-Universität Münster , Corrensstraße 40 , 48149 Münster , Germany.
J Am Chem Soc. 2019 Oct 16;141(41):16227-16231. doi: 10.1021/jacs.9b08960. Epub 2019 Oct 1.
Carbene insertion reactions with B-H bonds are a challenging but promising method for the synthesis of organoboranes. Herein, we report visible-light-induced B-H insertions of HBpin with acylsilane. This metal-free and operationally simple reaction proceeds in an atom-economical way with broad substrate scope under mild reaction conditions, affording a variety of important α-alkoxyorganoboronate esters in quantitative yields. Control experiments and density functional theory calculations suggest that the siloxycarbene generation from the T state of acylsilane and the carbene insertion into the B-H bond occurred in a concerted manner.
卡宾与B-H键的插入反应是一种具有挑战性但很有前景的有机硼烷合成方法。在此，我们报道了可见光诱导下频哪醇硼烷（HBpin）与酰基硅烷的B-H插入反应。这种无金属且操作简单的反应以原子经济的方式进行，在温和的反应条件下具有广泛的底物范围，能以定量产率得到多种重要的α-烷氧基硼酸酯。对照实验和密度泛函理论计算表明，酰基硅烷的T态产生硅氧基卡宾以及卡宾插入B-H键是协同发生的。
