External Electric Field—Phenyl interaction boosts hydrosilylation of substituted alkynes to α‐vinylsilane

Abstract

The hydrosilylation of terminal alkyne is the most straightforward and atom‐economy method to generate α‐vinylsilane. In the present paper, the acetylene and phenylacetylene hydrosilylation reactions were firstly studied by imposing external electric field (EEF) as a catalyst at the level of ωB97XD/TZVP. The results demonstrated that the oriented negative FY direction is the optimal direction, which mostly reduced the reaction barriers. Further computations indicated that the larger the EEF, the lower the barrier. When the EEF was increased to 180 (10−4) au, the barrier height of acetylene hydrosilylation (path Q) reduced almost 20 kcal/mol. To be surprised, as the phenyl substitute used, the hydrosilylation reaction (path FQ) was largely accelerated with the barrier height lowered to 13.2 kcal/mol, which decreased about 37 kcal/mol. Hopefully, this theoretical study would provide a guide for the experiment of the hydrosilylation of alkyne as much as possible.

Green Catalytic Method for Hydrothiolation of Allylamines: An External Electric Field

“…Since Shaik et al reported that the EEF controls the selectivity of iron-oxo porphyrin with propene, relevant literature studies gradually sprung up in theory and the experiment . Upon perusal of this work, we were inspired and tried to explore hydrofunctionalization reactions (such as hydroboration, hydrohydrazination, and hydrosilyation) by EEF as an “invisible” catalyst. According to this precedent, we first studied the EEF-mediated allylamine hydrothiolation reaction in this manuscript.…”