Amination of ethers using chloramine-T hydrate and a copper(I) catalyst

被引:67
作者
Albone, DP
Challenger, S
Derrick, AM
Fillery, SM
Irwin, JL
Parsons, CM
Takada, H
Taylor, PC [1 ]
Wilson, DJ
机构
[1] Univ Warwick, Dept Chem, Coventry CV4 7AL, W Midlands, England
[2] Pfizer Ltd, Cent Res, Sandwich CT13 9NJ, Kent, England
[3] AstraZeneca Pharmaceut, Mereside SK10 4TG, Alderley Pk, England
关键词
D O I
10.1039/b410883c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
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.
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收藏
页码:107 / 111
页数:5
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