New Bis(lithiomethyl)silanes: Building Blocks for Organosilanes

The first high yield preparation of non π‐stabilized bis(lithio‐methyl)silanes was performed by the reductive cleavage of C–S bonds with electron transfer reagents. Bis[(phenylthio)‐methyl]silanes synthesized by the reaction of dichlorosilanes with [(phenylthio)methyl]lithium were transformed to the corresponding bis(lithiomethyl)silanes 7 by reaction with lithium naphthalenide (LiC 10 H 8 ) or lithium p,p ′‐di‐ tert ‐butyl‐biphenylide (LiDBB) as an electron transfer reagent and were characterized by their reaction with Bu 3 SnCl. The C–S bonds of bis[(phenylthio)methyl]silanes can be cleaved selectively making possible the introduction of two different groups. – The silicon atom plays a central role in the reactivity of the presented structural types. The bis(lithiomethyl)silanes are used as new building blocks for the preparation of organosilanes, Si–H‐functionalized organosilanes, and 1,3‐disilacyclobutanes containing SiCH 2 Si structural units.