Catalytic silylation of O–nucleophiles via Si–H or Si–C bond cleavage: A route to silyl ethers, silanols and siloxanes

The silylation of various O–nucleophiles (e.g., alcohols, silanols, etc.) leads to desired and commonly used compounds such as silyl ethers (alkoxysilanes) or siloxanes. The most obvious and classical way for their preparation is based on the reaction of halosilanes with corresponding nucleophiles. This in turn touches on the vital issue of sustainable synthesis, additionally bearing in mind the selectivity and efficiency of the process. Taking all this into account, the development of sustainable and more atom-economical alternatives has gained considerable attention over the decades. This review will mainly detail solutions utilizing variously substituted silanes (as silylating agents), starting with highly accessible hydrosilanes, and finishing with those bearing vinyl, allyl or ethynyl functionalities. In the vast majority of cases, it covers the literature from the last twenty years (2001–2021), with due regard to previous historical results.