title: Rhodium(III)-catalyzed N-nitroso-directed C-H olefination of arenes. High-yield, versatile coupling under mild conditions.
abstract: N-nitroso compounds are a versatile class of organic structures that allow expedient access to a diversity of synthetically useful architectures through demonstrated reactivities. We report herein the development of a Rh(III)-catalyzed N-nitroso-directed methodology for the ortho-olefination of arenes. The heightened reactivity endowed by the N-nitroso group translates to mild reaction conditions, high reaction yields, and synthetic compatibility of otherwise elusive substrates (e.g., an unactivated olefin, 1-octene). Comprehensive mechanistic studies on the electronic effect, deuterium exchange, kinetic isotope effect, kinetic profile, and numerous Rh(III) complexes have established [RhCp*](2+) as the catalyst resting state, electrophilic C-H activation as the turnover-limiting step, and a five-membered rhodacycle as a catalytically competent intermediate. The ability to elaborate the N-nitroso moiety to an amine functionality provides a seminal example of the innumerable synthetic possibilities offered by this transformable directing group.
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China.
authors.forename: Baoqing
authors.initials: B
authors.lastname: Liu
authors.forename: Yang
authors.initials: Y
authors.lastname: Fan
authors.forename: Yang
authors.initials: Y
authors.lastname: Gao
authors.forename: Chao
authors.initials: C
authors.lastname: Sun
authors.forename: Cheng
authors.initials: C
authors.lastname: Xu
authors.forename: Jin
authors.initials: J
authors.lastname: Zhu
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D006841:Hydrocarbons, Aromatic; D009603:Nitroso Compounds; D009942:Organometallic Compounds; D012238:Rhodium