title: Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.
abstract: An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction.
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China). zhoubing2012@hotmail.com.
authors: Bing
authors: B
authors: Zhou
authors: Drug Discovery and Design Center, CAS Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China).
authors: Zhaoqiang
authors: Z
authors: Chen
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China). spyyx@163.com.
authors: Yaxi
authors: Y
authors: Yang
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China).
authors: Wen
authors: W
authors: Ai
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China).
authors: Huanyu
authors: H
authors: Tang
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China).
authors: Yunxiang
authors: Y
authors: Wu
authors: Drug Discovery and Design Center, CAS Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China). wlzhu@simm.ac.cn.
authors: Weiliang
authors: W
authors: Zhu
authors: Department of Medicinal Chemistry, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu Chong Zhi Road, Shanghai 201203 (PR China).
authors: Yuanchao
authors: Y
authors: Li
mesh_terms: D015057:1-Naphthylamine / Q000737:chemistry*; D000586:Amination; D000814:Aniline Compounds / Q000737:chemistry; D001391:Azo Compounds / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry; D008314:Malonates / Q000737:chemistry; D008333:Mandelic Acids / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D009589:Nitrogen Oxides / Q000737:chemistry*; D010084:Oxidation-Reduction; D012238:Rhodium / Q000737:chemistry*
chemical_list: D000814:Aniline Compounds; D001391:Azo Compounds; D007211:Indoles; D008314:Malonates; D008333:Mandelic Acids; D009589:Nitrogen Oxides; C057812:indoline; D006859:Hydrogen; D015057:1-Naphthylamine; D012238:Rhodium
keywords: CH activation; density functional calculations; heterocycles; nitrogen oxides; rhodium