Me₃Si−SiMe₂[oCON(iPr)₂−C₆H₄]: An Unsymmetrical Disilane Reagent for Regio‐ and Stereoselective Bis‐Silylation of Alkynes

Abstract

The air-stable unsymmetrical disilane Me 3 Si À SiMe 2 -[oCON(iPr) 2 C 6 H 4 ]h as been developed for bis-silylation of alkynes.T his reagent tolerates ar ange of functional groups, providing Z-vinyl disilanes in high yields.I ti sp roposed that the phenyl-ring-tethered amide group directs oxidative addition of Pd 0 into the Si À Si bond, which might facilitate formation of as ix-membered Pd cycle,g enerating products with good to excellent regioselectivity. Scheme 1. a) Bis-silylation of alkynesu sing traditional unsymmetrical disilanes activated by electronegative groups.b )Bis-silylation of alkynes using Me 3 SiÀSiMe 2 [oCON(iPr) 2 ÀC 6 H 4 ]( 1e). Key:t ransition metal (T.M.), regioselectivity ratio (r.r.).Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)–C(sp) by Ni complexes

“…In 2015, Spencer 14 reported intermolecular bis-silylation (hexamethyldisilane) catalysed by a palladium complex to construct cis -bis-silylation alkenes. In 2018, Song 15 used asymmetric disilane reagents for the region- and stereo-selective bis-silylation of alkynes. One Si-atom was connected to an amide group that could coordinate with transition metal Pd to achieve asymmetric di-silicification of terminal alkynes.…”