Unlocking Lewis acid–free metalation of O–nucleophiles in HFIP

Abstract Allylsilanes are primarily used in allylation reactions that form new C–C bonds. Although they can also serve as silylating reagents to generate Si–O bonds, such transformations have generally required Brønsted or Lewis acid catalysis. Herein, we describe an acid-free method to access silyl ethers, siloxanes, and borasiloxanes via silylation or borylation. Hexafluoroisopropanol enables this reactivity, allowing a wide range of alcohols and silanols to undergo efficient conversion under mild conditions.