Sodium Hydroxide Catalyzed Dehydrocoupling of Alcohols with Hydrosilanes

Anton A. Toutov, Kerry N. Betz, Michael C. Haibach, Andrew M. Romine, and Robert H. Grubbs

Organic Letters,
2016, 18, (22), 5776-5779; DOI: 10.1021/acs.orglett.6b01687


A large number of catalytic methods for the construction of O− Si bonds have been developed: the direct silylation of alcohols by transition-metal catalysis, Brønsted and Lewis acids/bases, and catalytic hydrosilylation of carbonyl compounds have been the most commonly employed protocols.

However, despite decades of work, the most straightforward method for the construction of the O−Si bond is the treatment of alcohols with moisture-sensitive chlorosilanes in the presence of nucleophilic catalysts and a base to scavenge the HCl generated. Now, the Grubbs group at Caltech has reported that the dehydrocoupling of alcohols and silanes can be achieved with NaOH as the catalyst.

The method has excellent scope in both the hydrosilane and the alcohol and proceeds under mild and convenient conditions to enable access to silyl ethers for protecting and directing group chemistries, materials science applications, and a variety of other purposes.

Author: Anton Toutov