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We report the first diarylborane-catalysed hydrosilylation of epoxides and cyclic ethers. Mechanistic studies on the in situ generated Piers’ borane (C6F5)2BH with hydrosilanes in the presence of an epoxide revealed that an alkyloxy(diaryl)borane (C6F5)2BOR is readily formed as a catalytically competent species for the outer-sphere hydrosilylation of epoxides and cyclic ethers.

Graphical abstract: Piers’ borane-mediated hydrosilylation of epoxides and cyclic ethers

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