title: Catalytic migratory oxidative coupling of nitrones through an outer-sphere C(sp3)-H activation process.
abstract: Outer-sphere redox catalysis is key to efficient C-H activation, which has attracted increased interest in organic chemistry. In this account, we describe a Cu(I) -catalyzed oxidative coupling between nitrones and various ethers or amines as an example. Predictable site-selective C-C bond formation was achieved through activation of the C-H bonds in each coupling partner and the migration of a C-N double bond. Mechanistic studies strongly suggested that the reaction proceeded via an oxonium/iminium cation species as the key intermediate. The mechanistic information allows for future extension of outer-sphere redox catalysis.
authors: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1, Hongo, Tokyo 113-0033, Japan.
authors: Shogo
authors: S
authors: Hashizume
authors: Kounosuke
authors: K
authors: Oisaki
authors: Motomu
authors: M
authors: Kanai
mesh_terms: D000588:Amines / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry; D015394:Molecular Structure; D009589:Nitrogen Oxides / Q000138:chemical synthesis / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000588:Amines; D004987:Ethers; D009589:Nitrogen Oxides; D009942:Organometallic Compounds; C015388:nitrones; D003300:Copper