title: The application of intramolecular radical cyclizations of acylsilanes in the regiospecific formation of cyclic silyl enol ethers.
abstract: Acylsilanes with terminal alpha-stannyl bromide or xanthate functionalities are prepared. Alpha-stannyl radicals generated from these acylsilanes undergo intramolecular cyclizations to give cyclic silyl enol ethers regiospecifically. The radical processes involve radical cyclization, Brook rearrangement, and beta-fragmentation in sequence. A tributylstannyl group serves as the radical leaving group. The newly formed sigma-bond and pi-bond are located between the same two carbon atoms. This approach is limited to the formation of five-membered rings. In another route, omega-bromo-alpha-phenylsulfonylacylsilanes are synthesized. The radical cyclizations of these alpha-sulfonylacylsilanes also give cyclic silyl enol ethers. The phenylsulfonyl moiety is the radical leaving group in this system. Furthermore, the newly formed sigma-bond and pi-bond are located at adjacent positions sharing a single carbon atom. The latter approach is effective for both five- and six-membered ring formation.
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China.
authors.forename: C H
authors.initials: CH
authors.lastname: Huang
authors.forename: S Y
authors.initials: SY
authors.lastname: Chang
authors.forename: N S
authors.initials: NS
authors.lastname: Wang
authors.forename: Y M
authors.initials: YM
authors.lastname: Tsai