title: Iridium-catalyzed asymmetric ring-opening of azabicyclic alkenes with alcohols.
abstract: A novel asymmetric ring-opening reaction of N-substituted azabenzonorbornadienes with a wide variety of substituted benzyl alcohols and the addition reaction of N-substituted azabenzonorbornadienes with thiols are reported, affording the corresponding 1,2-trans-alkoxyamino products in moderate yields with excellent enantioselectivities (up to 94% ee) and the corresponding thiol addition products in high yields with lower enantiomeric excesses (ee) in the presence of iridium catalyst, respectively. The effects of ligands, catalyst loading, solvents and additives, and temperature were also investigated. The anti-configuration of the product 3c was confirmed by X-ray crystal structure analysis. A possible mechanism for the present catalytic reaction is proposed.
authors.affiliation: Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China. yangdq@scnu.edu.cn
authors.forename: Dingqiao
authors.initials: D
authors.lastname: Yang
authors.forename: Jiuyun
authors.initials: J
authors.lastname: Xia
authors.forename: Yuhua
authors.initials: Y
authors.lastname: Long
authors.forename: Zhongyi
authors.initials: Z
authors.lastname: Zeng
authors.forename: Xiongjun
authors.initials: X
authors.lastname: Zuo
authors.forename: Sanyong
authors.initials: S
authors.lastname: Wang
authors.forename: Chunrong
authors.initials: C
authors.lastname: Li
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D002384:Catalysis; D007495:Iridium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D000438:Alcohols; D000475:Alkenes; D000588:Amines; D001372:Aza Compounds; D001643:Bridged Bicyclo Compounds; D009942:Organometallic Compounds; D007495:Iridium