Unlocking Lewis acid-free metalation of O-nucleophiles in HFIP.

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.