title: Asymmetric total synthesis of (-)-lingzhiol via a Rh-catalysed [3+2] cycloaddition.
abstract: The development of efficient reactions for the one-pot construction of bicyclic ring systems bearing two quaternary carbon centres at their bridgehead positions represents a significant challenge to synthetic chemistry. The development of new methods capable of overcoming this challenge is highly desirable, because this motif can be found in a wide range of natural products with significant biological activities. Herein, we report an efficient [3+2] cycloaddition reaction between an enal and an alleno rhodium species, which was generated in situ from the corresponding enynol via a retro metal-propargylation reaction, to give [3.3.0] and [3.4.0] bicyclic systems bearing two quaternary atoms at their bridgehead positions. The developed chemistry has been successfully applied to the asymmetric total synthesis of natural product (-)-lingzhiol (4) for the first time in 17 steps.
authors.affiliation: 1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China [3].
authors.forename: Rong
authors.initials: R
authors.lastname: Long
authors.affiliation: 1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China [3].
authors.forename: Jun
authors.initials: J
authors.lastname: Huang
authors.affiliation: 1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China.
authors.forename: Wenbin
authors.initials: W
authors.lastname: Shao
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China.
authors.forename: Song
authors.initials: S
authors.lastname: Liu
authors.affiliation: School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Lan
authors.affiliation: 1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China.
authors.forename: Jianxian
authors.initials: J
authors.lastname: Gong
authors.affiliation: 1] Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China [2] Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science (BNLMS), and Peking-Tsinghua Center for Life Sciences and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China [3] Key Laboratory of Marine Drugs, Chinese Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, 5 Yushan Road, Qingdao 266003, China.
authors.forename: Zhen
authors.initials: Z
authors.lastname: Yang
mesh_terms: D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D061565:Cycloaddition Reaction / Q000379:methods*; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D010720:Phosphines; D013729:Terpenes; C587942:lingzhiol; D002244:Carbon; D012238:Rhodium