title: Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids.
abstract: Meliacarpin-type limonoids are an important class of organic insecticides. Their syntheses are challenging due to their chemical complexity. Here, we report the highly enantio- and diastereoselective synthesis of the left fragments of azadirachtin I and 1-cinnamoylmelianolone, being two important family members of meliacarpin-type limonoids, via pairwise palladium- and gold-catalyzed cascade reactions. Gold-catalyzed reactions of 1,7-diynes were performed as model studies, and the efficient construction of tetracyclic late-stage intermediates was achieved on the basis of this key transformation. Our unique route gave both of the left fragments in 23 steps from the commercially available chiral starting material (-)-carvone. This study significantly advances research on the synthesis of the meliacarpin-type limonoids.
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Hang
authors.initials: H
authors.lastname: Shi
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Ceheng
authors.initials: C
authors.lastname: Tan
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Weibin
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Zichun
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Rong
authors.initials: R
authors.lastname: Long
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
authors.forename: Jianxian
authors.initials: J
authors.lastname: Gong
authors.affiliation: State Key Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, and Peking-Tsinghua Center for Life Sciences, Peking University , Beijing 100871, China.
authors.forename: Tuoping
authors.initials: T
authors.lastname: Luo
authors.affiliation: Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.|State Key Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, and Peking-Tsinghua Center for Life Sciences, Peking University , Beijing 100871, China.|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: D002384:Catalysis; D053280:Diynes / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D036701:Limonins / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D053280:Diynes; D036701:Limonins; D006046:Gold; C010329:azadirachtin