title: Organocatalytic, Asymmetric Total Synthesis of (-)-Haliclonin A.
abstract: The first total synthesis of the alkaloid (-)-haliclonin A is reported. The asymmetric synthesis relied on a novel organocatalytic asymmetric conjugate addition of nitromethane with 3-alkenyl cyclohex-2-enone to set the stereochemistry of the all-carbon quaternary stereogenic center. The synthesis also features a Pd-promoted cyclization to form the 3-azabicyclo[3,3,1]nonane core, a SmI2 -mediated intermolecular reductive coupling of enone with aldehyde to form the requisite secondary chiral alcohol, ring-closing alkene and alkyne metathesis reactions to build the two aza-macrocyclic ring systems, and an unprecedented direct transformation of enol into enone.
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Lian-Dong
authors.initials: LD
authors.lastname: Guo
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Xiong-Zhi
authors.initials: XZ
authors.lastname: Huang
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Shi-Peng
authors.initials: SP
authors.lastname: Luo
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Wen-Sen
authors.initials: WS
authors.lastname: Cao
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Yuan-Ping
authors.initials: YP
authors.lastname: Ruan
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
authors.forename: Jian-Liang
authors.initials: JL
authors.lastname: Ye
authors.affiliation: Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China. pqhuang@xmu.edu.cn.|State Key Laboratory of Applied Organic Chemistry Lanzhou University, Lanzhou, 730000, P.R. China. pqhuang@xmu.edu.cn.
authors.forename: Pei-Qiang
authors.identifier: http://orcid.org/0000-0003-3230-0457
authors.initials: PQ
authors.lastname: Huang
mesh_terms: D002384:Catalysis; D003959:Diamines / Q000138:chemical synthesis*; D047028:Macrocyclic Compounds / Q000138:chemical synthesis*
chemical_list: D003959:Diamines; D047028:Macrocyclic Compounds; C540232:haliclonin A
keywords: alkaloids; macrocycles; metathesis; natural products; total synthesis