81499-28-7Relevant academic research and scientific papers
Copper-Catalyzed Radical N-Demethylation of Amides Using N-Fluorobenzenesulfonimide as an Oxidant
Yi, Xuewen,Yi, Xuewen,Lei, Siyu,Liu, Wangsheng,Che, Fengrui,Yu, Chunzheng,Liu, Xuesong,Wang, Zonghua,Zhou, Xin,Zhang, Yuexia
supporting information, p. 4583 - 4587 (2020/05/05)
An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.
The Geometry of Displacements at Nonstereogenic Atoms: The Formal Displacement of Alkoxide from Alkoxyamines by Organolithium Reagents
Beak, Peter,Basha, Anwer,Kokko, Bruce,Loo, DeKai
, p. 6016 - 6023 (2007/10/02)
Amination of organolithium regents can be achieved by reaction with methyllithium-alkoxyamines.Details of the methodology and analysis of the reaction mechanism are presented.Reactions of methyl-, ethyl-, n-butyl-, sec-butyl-, tert-butyl-, phenyl-, and (o-methoxyphenyl)lithium with methyllithium-methoxyamine give the corresponding amines, isolated as the benzamides, in yields of 71-97percent.Lower yields are obtained with o-lithio-N,N-diisopropylbenzamide, 4-lithiodibenzothiophene, n-butylmagnesium bromide, and phenylmagnesium bromide.Reactions of n-butyl, sec-butyl-, tert-butyl-, and phenyllithium with methyllithium-N-methylmethoxyamine provide the corresponding N-methyl-amines, isolated as the benzamides, in yields of 30-70percent.Retention of the N-methyl group in these reactions is considered to rule out a nitrene intermediate.Involvement of a lithium alkoxyamide is suggested by the formation and substitution of that species by two different routes.Dilithiation of N-methoxy-N-amine (17) gives, after an intramolecular reaction and addition of acetyl chloride, N-acetylindoline, in 78percent yield.Dilithiation of N-methyl-N-amine (19) gives N-methyl-N-acetamide (20), after rection with acetyl chloride.The nitrogen transfer in this conversion is shown by a double labeling experiment to be intermolecular.This results is taken to suggest that the bond angles required for displacement cannot be achieved in a six-membered ring, and the mechanism of the reaction involves a complex in which displacement occurs via an SN2-like transition state.The exocyclic-endocyclic intramolecular-intermolecular test is noted to provide a general approach for determination of the geomatry of reactions at nonstereogenic centers.
