title: Amination of ethers using chloramine-T hydrate and a copper(I) catalyst.
abstract: Amination of C-H bonds activated by ether oxygen atoms is facile with chloramine-T as nitrene source and copper(I) chloride in acetonitrile as catalyst. For cyclic ethers the hemiaminal products are generally stable and can be isolated pure. For acyclic ethers, the hemiaminal products, as expected, fragment with elimination of alcohol to yield imines. When activation of benzylic positions is remote through a conjugated system, stable benzylamine derivatives are isolated. Mechanistic studies are consistent with concerted insertion of an electrophilic nitrenoid into the C-H bond in the rate-determining step, though in an asynchronous manner with a more activated substrate.
authors.affiliation: Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.
authors.forename: David P
authors.initials: DP
authors.lastname: Albone
authors.forename: Stephen
authors.initials: S
authors.lastname: Challenger
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Derrick
authors.forename: Shaun M
authors.initials: SM
authors.lastname: Fillery
authors.forename: Jacob L
authors.initials: JL
authors.lastname: Irwin
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Parsons
authors.forename: Hiroya
authors.initials: H
authors.lastname: Takada
authors.forename: Paul C
authors.initials: PC
authors.lastname: Taylor
authors.forename: D James
authors.initials: DJ
authors.lastname: Wilson
mesh_terms: D000586:Amination; D002384:Catalysis; D002700:Chloramines / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism; D014105:Tosyl Compounds / Q000737:chemistry*
chemical_list: D002700:Chloramines; D004987:Ethers; D014105:Tosyl Compounds; C016300:chloramine-T; D003300:Copper