Amination of ethers using chloramine-T hydrate and a copper(I) catalyst.
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.
Albone
David P
DP
Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.
Challenger
Stephen
S
Derrick
Andrew M
AM
Fillery
Shaun M
SM
Irwin
Jacob L
JL
Parsons
Christopher M
CM
Takada
Hiroya
H
Taylor
Paul C
PC
Wilson
D James
DJ
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*
D002700:Chloramines; D004987:Ethers; D014105:Tosyl Compounds; C016300:chloramine-T; D003300:Copper