title: Total Syntheses of the Tetracyclic Cyclopiane Diterpenes Conidiogenone, Conidiogenol, and Conidiogenone B.
abstract: Total syntheses of the biologically important and structurally unique tetracyclic diterpenes conidiogenone, conidiogenol, and conidiogenone B of the cyclopiane class are reported. The absolute configuration of naturally occurring conidiogenone B was also corrected. The key step of our strategy involved the highly efficient construction of both ring C and the quaternary carbon center shared by rings A and C through a one-step regioselective and diastereoselective cycloenlargement in the form of a semipinacol-type rearrangement. In particular, the desired regioselectivity was made possible by properly adjusting the migratory aptitude of the migrating carbon atom through the introduction of an electron-donating phenylthio group at this position.
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Si-Hua
authors.initials: SH
authors.lastname: Hou
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China. tuyq@lzu.edu.cn, tuyq@sjtu.edu.cn.|School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, P.R. China. tuyq@lzu.edu.cn, tuyq@sjtu.edu.cn.|Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, P.R. China. tuyq@lzu.edu.cn, tuyq@sjtu.edu.cn.
authors.forename: Yong-Qiang
authors.initials: YQ
authors.lastname: Tu
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Shuang-Hu
authors.initials: SH
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Chao-Chao
authors.initials: CC
authors.lastname: Xi
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Fu-Min
authors.initials: FM
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Shao-Hua
authors.initials: SH
authors.lastname: Wang
authors.affiliation: School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, P.R. China.
authors.forename: Yan-Tao
authors.initials: YT
authors.lastname: Li
authors.affiliation: State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, P.R. China.
authors.forename: Lin
authors.initials: L
authors.lastname: Liu
mesh_terms: D018360:Crystallography, X-Ray; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
chemical_list: D004224:Diterpenes
keywords: cyclization; natural products; semipinacol rearrangement; tetracyclic diterpenes; total synthesis