title: Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes.
abstract: A copper-catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker-type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β-hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess-Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di- and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical-organometallic mechanism involving an amidyl radical cyclization to form the key C-N bond.
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Peng
authors.initials: P
authors.lastname: Xiong
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Fan
authors.initials: F
authors.lastname: Xu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Xiang-Yang
authors.initials: XY
authors.lastname: Qian
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China.
authors.forename: Yared
authors.initials: Y
authors.lastname: Yohannes
authors.affiliation: Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, P. R. China.
authors.forename: Jinshuai
authors.initials: J
authors.lastname: Song
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China. xinlu@xmu.edu.cn.
authors.forename: Xin
authors.initials: X
authors.lastname: Lu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Material, State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Xiamen University, Xiamen, 361005, P. R. China. haichao.xu@xmu.edu.cn.
authors.forename: Hai-Chao
authors.identifier: http://orcid.org/0000-0002-3008-5143
authors.initials: HC
authors.lastname: Xu
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006827:Hydantoins / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D023303:Oxazolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry
chemical_list: D000475:Alkenes; D006827:Hydantoins; D008024:Ligands; D023303:Oxazolidinones; D010165:Palladium; D003300:Copper
keywords: copper; cyclization; oxidation; radicals; synthetic methods