Custom Hydrosilane Synthesis Based on Monosilane

The omnipresence of silicon compounds with carbon substituents in synthetic chemistry hides the fact that, except for certain substitution patterns at the silicon atom, their preparation is often far from trivial. The challenge is rooted in the lack of control over nucleophilic substitution with carbon nucleophiles at silicon atoms with three or four leaving groups. For example, SiCl4 usually converts into intractable mixtures of chlorosilanes, typically requiring several distillation cycles to reach high purity. Accordingly, there is no universal approach to silanes with heteroleptic substitution. Here, using a bench-stable SiH4 surrogate, we introduce a general strategy for the on-demand synthesis of silicon compounds decorated with different aryl and alkyl substituents. Reliable protocols are the basis of the selective and programmable synthesis of dihydro- and monohydrosilanes; aryl-substituted trihydrosilanes are also accessible in a straightforward fashion. These otherwise difficult-to-access hydrosilanes are only three or fewer easy synthetic operations away from the SiH4 surrogate.