Oxyallyl Cation Capture via Electrophilic Deborylation of Organoboronates: Access to α,α'-Substituted Cyclic Ketones.

An umpolung strategy to synthesize α,α'-substituted cyclic ketones through the nucleophilic addition of organoboronates to α-hydroxyl silyl enol ethers is described. The reaction proceeds via the trapping of in situ generated oxyallyl cations via the electrophilic deborylation of C(sp2) and C(sp) borates. This efficient and straightforward method provides direct access to α-substituted silyl enol ethers in high yield with complete regioselectivity. Desilylation in a one-pot procedure provides the corresponding α,α'-disubstituted ketones with high diastereoselectivity.