title: Iodoarene-Catalyzed Stereospecific Intramolecular sp(3) C-H Amination: Reaction Development and Mechanistic Insights.
abstract: A new strategy is reported for intramolecular sp(3) C-H amination under mild reaction conditions using iodoarene as catalyst and m-CPBA as oxidant. This C-H functionalization involving iodine(III) reagents generated in situ occurs readily at sterically hindered tertiary C-H bonds. DFT (M06-2X) calculations show that the preferred pathway involves an iodonium cation intermediate and proceeds via an energetically concerted transition state, through hydride transfer followed by the spontaneous C-N bond formation. This leads to the experimentally observed amination at a chiral center without loss of stereochemical information.
authors.affiliation: †State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
authors.forename: Chendan
authors.initials: C
authors.lastname: Zhu
authors.forename: Yong
authors.initials: Y
authors.lastname: Liang
authors.forename: Xin
authors.initials: X
authors.lastname: Hong
authors.affiliation: †State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
authors.forename: Heqing
authors.initials: H
authors.lastname: Sun
authors.affiliation: †State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
authors.forename: Wei-Yin
authors.initials: WY
authors.lastname: Sun
authors.forename: K N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: †State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
authors.forename: Zhuangzhi
authors.initials: Z
authors.lastname: Shi
mesh_terms: D000586:Amination; D002384:Catalysis; D002723:Chlorobenzoates / Q000737:chemistry*; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007455:Iodine / Q000737:chemistry*; D008958:Models, Molecular; D016877:Oxidants / Q000737:chemistry*
chemical_list: D002723:Chlorobenzoates; D006841:Hydrocarbons, Aromatic; D016877:Oxidants; D007455:Iodine; C000433:3-chloroperbenzoic acid