103794-57-6Relevant articles and documents
One-pot synthesis of alkoxyamine derivatives by reductive alkoxyamination with a 2-picoline-borane complex
Kawase, Yasushi,Yamagishi, Takehiro,Kutsuma, Teruo,Ueda, Kimio,Iwakuma, Takeo,Nakata, Tadashi,Yokomatsu, Tsutomu
scheme or table, p. 463 - 470 (2009/06/08)
Reduction of oxime ethers with a 2-picoline-borane complex was examined to give alkoxyamine derivatives. The reduction was found to proceed in the presence of aqueous HCl in MeOH-AcOH. The method was extended to one-pot synthesis of alkoxyamine derivative
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.
THE ELECTROPHILIC AMINATION OF ORGANOLITHIUMS WITH METHYLLITHIUM COMPLEXES OF N-SUBSTITUTED METHOXYAMINES
Kokko, Bruce J.,Beak, Peter
, p. 561 - 564 (2007/10/02)
Three N-alkyl methoxyamine derivatives are shown to be effective as electrophilic reagents for the conversion of organolithiums to secondary amines.
