Me 3 Si−SiMe 2 [ o CON( i Pr) 2 −C 6 H 4 ]: An Unsymmetrical Disilane Reagent for Regio‐ and Stereoselective Bis‐Silylation of Alkynes

The air‐stable unsymmetrical disilane Me 3 Si−SiMe 2 [ o CON( i Pr) 2 C 6 H 4 ] has been developed for bis‐silylation of alkynes. This reagent tolerates a range of functional groups, providing Z ‐vinyl disilanes in high yields. It is proposed that the phenyl‐ring‐tethered amide group directs oxidative addition of Pd 0 into the Si−Si bond, which might facilitate formation of a six‐membered Pd cycle, generating products with good to excellent regioselectivity.