title: Scalable Total Synthesis of rac-Jungermannenones B and C.
abstract: Reported is the first scalable synthesis of rac-jungermannenones B and C starting from the commercially available and inexpensive geraniol in 10 and 9 steps, respectively. The unique jungermannenone framework is rapidly assembled by an unprecedented regioselective 1,6-dienyne reductive cyclization reaction which proceeds through a vinyl radical cyclization/allylic radical isomerization mechanism. DFT calculations explain the high regioselectivity observed in the 1,6-dienyne reductive radical cyclization.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Synthetic and Functional Biomolecules Center, Peking-Tsinghua Center for Life Sciences, Peking University, Beijing, 100871, China.|National Institute of Biological Sciences (NIBS), Beijing, 102206, China.
authors.forename: Weilong
authors.initials: W
authors.lastname: Liu
authors.affiliation: National Institute of Biological Sciences (NIBS), Beijing, 102206, China.
authors.forename: Houhua
authors.initials: H
authors.lastname: Li
authors.affiliation: College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
authors.forename: Pei-Jun
authors.initials: PJ
authors.lastname: Cai
authors.affiliation: National Institute of Biological Sciences (NIBS), Beijing, 102206, China.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Wang
authors.affiliation: College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
authors.forename: Zhi-Xiang
authors.initials: ZX
authors.lastname: Yu
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Synthetic and Functional Biomolecules Center, Peking-Tsinghua Center for Life Sciences, Peking University, Beijing, 100871, China. xglei@pku.edu.cn.|National Institute of Biological Sciences (NIBS), Beijing, 102206, China. xglei@pku.edu.cn.
authors.forename: Xiaoguang
authors.initials: X
authors.lastname: Lei
mesh_terms: D000080462:Acyclic Monoterpenes; D003500:Cyclization; D004224:Diterpenes / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D013729:Terpenes / Q000737:chemistry*
chemical_list: D000080462:Acyclic Monoterpenes; D004224:Diterpenes; D013729:Terpenes; C000611349:jungermannenone b; C000611350:jungermannenone c; C007836:geraniol
keywords: cyclizations; dienynes; natural products; terpenoids; total synthesis