title: Efficient Access to Bicyclo[4.3.0]nonanes: Copper-Catalyzed Asymmetric Silylative Cyclization of Cyclohexadienone-Tethered Allenes.
abstract: The creation of three consecutive chiral carbon centers in one step is achieved using Cu-catalyzed asymmetric silylative cyclization of cyclohexadienone-tethered allenes. Through regioselective β-silylation of the allene and subsequent enantioselective 1,4-addition to cyclohexadienone, this tandem reaction could afford cis-hydrobenzofuran, cis-hydroindole, and cis-hydroindene frameworks with excellent yields (80-98%) and enantioselectivities (94-98% ee) bearing vinylsilane and enone substructures. Meanwhile, this mild transformation is generally compatible with a wide range of functional groups, which allows further conversion of the bicyclic products to bridged and tricyclic ring structures.
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Zhi-Tao
authors.initials: ZT
authors.lastname: He
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Xiao-Qi
authors.initials: XQ
authors.lastname: Tang
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Li-Bo
authors.initials: LB
authors.lastname: Xie
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Mian
authors.initials: M
authors.lastname: Cheng
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China). tianping@sioc.ac.cn.
authors.forename: Ping
authors.initials: P
authors.lastname: Tian
authors.affiliation: CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Guo-Qiang
authors.initials: GQ
authors.lastname: Lin
keywords: allenes; asymmetric synthesis; copper; cyclization; silylation