Bis-silylation of internal alkynes enabled by Ni(0) catalysis

1,2-Bis-silyl alkenes have exciting synthetic potential for programmable sequential synthesis via manipulation of the two vicinal silyl groups. Transition metal-catalyzed bis-silylation of alkynes with disilanes is the most straightforward strategy to access such useful building blocks. However, this process has some limitations: (1) symmetric disilanes are frequently employed in most of the reactions to assemble two identical silyl groups, which makes chemoselective differentiation for stepwise downstream transformations difficult; (2) the main catalysts are low-valent platinum group transition metal complexes, which are expensive; and (3) internal alkynes remain challenging substrates with low inherent reactivity. Thus, the development of abundant metal-catalyzed bis-silylation of internal alkynes with unsymmetrical disilanes is of significance. Herein, we solve most of the aforementioned limitations in bis-silylation of unsaturated bonds by developing a strongly coordinating disilane reagent and a Ni(0) catalytic system. Importantly, we sufficiently realize the stepwise recognition of the two silyl groups, making this synthetic protocol of wide potential utility. Bis-silylated alkenes offer the advantage of two functional handles with distinguished reactivity for downstream functionalization. Here, the authors report a nickel-catalyzed bis-silylation of internal alkynes to versatile silylated alkene intermediates which can be chemoselectively manipulated.

Automated summary

This study presents a nickel-catalyzed bis-silylation of internal alkynes to generate versatile silylated alkene intermediates, which can be selectively manipulated for downstream functionalization.