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

• Published in: Nature communications Vol. 12; no. 1; p. 68
• Main Authors: Zhang, Yun, Wang, Xi-Chao, Ju, Cheng-Wei, Zhao, Dongbing
• Format: Journal Article
• Language: English
• Published: England Nature Publishing Group 04.01.2021; Nature Publishing Group UK; Nature Portfolio
• Subjects: Alkenes; Alkynes; Bonding strength; Catalysis; Catalysts; Coordination compounds; Intermediates; Ligands; Metal complexes; Nickel; Platinum; Reagents; Substrates; Transition metal compounds
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-20392-w

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.