19219-50-2Relevant academic research and scientific papers
Efficient nickel-catalysed: N -alkylation of amines with alcohols
Afanasenko, Anastasiia,Elangovan, Saravanakumar,Stuart, Marc C. A.,Bonura, Giuseppe,Frusteri, Francesco,Barta, Katalin
, p. 5498 - 5505 (2018/11/20)
The selective N-alkylation of amines with alcohols via the borrowing hydrogen strategy represents a prominent sustainable catalytic method, which produces water as the only by-product and is ideally suited for the catalytic transformation of widely available alcohol reaction partners that can be derived from renewable resources. Intensive research has been devoted to the development of novel catalysts that are mainly based on expensive noble metals. However, the availability of homogeneous or heterogeneous non-precious metal catalysts for this transformation is very limited. Herein we present a highly active and remarkably easy-to-prepare Ni based catalyst system for the selective N-alkylation of amines with alcohols, that is in situ generated from Ni(COD)2 and KOH under ligand-free conditions. This novel method is very efficient for the functionalization of aniline and derivatives with a wide range of aromatic and aliphatic alcohols as well as diols and exhibits excellent functional group tolerance including halides, benzodioxane and heteroaromatic groups. Several TEM measurements combined with elemental analysis were conducted in order to gain insight into the nature of the active catalyst and factors influencing reactivity.
A general procedure to selectively prepare N-alkylanilines by an unexpected reaction of (Z)-(tert-butylsulfanyl)(aryl)diazenes with alkyllithium reagents
Barbero, Margherita,Degani, Iacopo,Dughera, Stefano,Fochi, Rita
, p. 742 - 750 (2007/10/03)
A general procedure has been set up to prepare, selectively, the N-monoalkylanilines 7, reacting (Z)-(tert-butylsulfanyl)(aryl)diazenes 3 with alkyllithium 6 (MeLi, BuLi, s-BuLi, n-C6H13Li). The reactions were carried out in anhydrous diethyl ether at 0°C or - 78°C, depending on the reagent 6, and then at room temperature. In optimal conditions the yields of the pure products 7 (uncontaminated by dialkylation products) were from good to excellent: for 38 considered examples, 34 were positive with yields varying between 61percent and 91percent (average yield 78percent). Collateral proofs were carried out to support a hypothesized reaction mechanism.
