Lewis‐Acid‐Catalyzed Direct Nucleophilic Substitution Reaction of Alcohols for the Functionalization of Aromatic Amines

Abstract

N‐Alkylation of aromatic amines with alcohols is an efficient route for the synthesis of higher benzylamines. Herein, we explore an efficient catalytic activity of tin(ii) triflate for the N‐alkylation of secondary anilines with alcohols for the synthesis of tertiary benzylamines. Mechanistic studies suggest that the developed protocol follows direct nucleophilic substitution pathway instead of imine or enamine pathway. The developed method is also useful for the synthesis of secondary amines as well as late stage functionalization of naturally occurring alcohols.

Zirconium-catalysed direct substitution of alcohols: enhancing the selectivity by kinetic analysis

“…[28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] Despite this, this catalyst class is hardly represented in the context of dehydrative substitution of alcohols in contrast to its trivalent (and bivalent) counterparts. [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60] In direct etherification, two alcohols are joined with loss of water. To enable the formation of unsymmetrical ethers from two different alcohols, the transformation typically relies on one alcohol being more electrophilic than the other, e.g.…”

Sulfamic acid functionalized PVC: a remarkably efficient heterogeneous reusable catalyst for the acid-catalyzed reactions

“…99.9%) owing to its high acid density and highly exposed sulfamic acid sites. Notably, the ketal yield and acid density gradually decreases from 99.9% to 89.5% and 2.12 to 1.93 mmolg -1 with PVC-DTA-SO3H to PVC-PHA-SO3H, respectively, which should be due to a fact that the increase of the steric hindrance of the amination reagent reduced the nucleophilic substitution reaction activity of the amino group with PVC [54][55][56][57] and the growth of the amino-linked carbon chain reduces its nucleophilic ability [58,59], resulting in a decrease in the number of amino groups grafted on the PVC carbon chain, which eventually led to a decrease in the number of sulfonic acid groups connected by the chlorosulfonation reaction.…”

General Synthesis of N-Alkylation of Amines with Secondary Alcohols via Hydrogen Autotransfer

“…To date, the N -alkylation of anilines with primary alcohols have been well-explored by using various base-metal (Mn, Fe, Co, and Ni) catalysts . On the other hand, seminal examples based on noble-metal catalyzed homogeneous and heterogeneous supported catalyst systems were reported for the secondary alcohol amination reactions.…”