title: Asymmetric Synthesis of Axially Chiral Isoquinolones: Nickel-Catalyzed Denitrogenative Transannulation.
abstract: The first Ni(0)/bis(oxazoline)-catalyzed asymmetric denitrogenative transannulation of 1,2,3-benzotriazin-4(3H)-ones with bulky internal alkynes to form novel axially chiral isoquinolones in an atroposelective manner has been developed. This method provides direct asymmetric access to axially chiral isoquinolones with excellent functional-group tolerance in excellent yields and stereoselectivities from readily available starting materials under mild reaction conditions. These axially chiral isoquinolones exhibit high cytotoxicity against a number of human cancer cell lines. DFT calculations reveal the nature of the transition state in the key annulation step.
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055 (P.R. China).
authors.forename: Zhi-Jia
authors.initials: ZJ
authors.lastname: Fang
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055 (P.R. China).
authors.forename: Sheng-Cai
authors.initials: SC
authors.lastname: Zheng
authors.affiliation: College of Materials Science & Engineering, Taiyuan University of Technology, Shanxi (P.R. China).
authors.forename: Zhen
authors.initials: Z
authors.lastname: Guo
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055 (P.R. China).
authors.forename: Jing-Yao
authors.initials: JY
authors.lastname: Guo
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055 (P.R. China). tanb@sustc.edu.cn.
authors.forename: Bin
authors.initials: B
authors.lastname: Tan
authors.affiliation: Department of Chemistry, South University of Science and Technology of China, Shenzhen, 518055 (P.R. China). liuxy3@sustc.edu.cn.
authors.forename: Xin-Yuan
authors.initials: XY
authors.lastname: Liu
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D007546:Isoquinolines / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010080:Oxazoles / Q000737:chemistry; D013237:Stereoisomerism; D014227:Triazines / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D000480:Alkynes; D007546:Isoquinolines; D010080:Oxazoles; D014227:Triazines; D009532:Nickel; C102393:1,2,3-benzotriazin-4-one
keywords: annulations; chirality; density functional calculations; heterocycles; nickel