Preparation of α‐Mono‐Fluoromethyl Silanes via Nucleophilic Displacement on Chlorosilanes With LiCH2F

Though surprising – when compared with well-established poly-fluoromethyl silanes (e.g., Ruppert-Prakash reagent, TMSCF3) – α-mono-fluoromethyl silanes are underrepresented motifs in chemical synthesis, having been – so far – reported no more than 2–3 examples. We propose herein the nucleophilic substitution on the silicon atom of chlorosilanes – with fluoromethyllithium (LiCH2F) – as a general strategy for their direct preparation. The procedure - exhibiting remarkable dependance on steric elements across silicon – can be advantageously extended to prepare distinct IV-row heteroatom-centered analogues such as tin and germanium organometallics.