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Synthesis 2018; 50(23): 4617-4626
DOI: 10.1055/s-0037-1610252
DOI: 10.1055/s-0037-1610252
paper
Efficient and Versatile Catalytic Systems for the N-Methylation of Primary Amines with Methanol Catalyzed by N-Heterocyclic Carbene Complexes of Iridium
Authors
This work was supported by JSPS KAKENHI Grant Number JP16H01018 and JP18H04255 in Precisely Designed Catalysts with Customized Scaffolding and Nagase Science and Technology Foundation.
Further Information
Publication History
Received: 25 May 2018
Accepted after revision: 25 July 2018
Publication Date:
30 August 2018 (online)
Abstract
Efficient and versatile catalytic systems were developed for the N-methylation of both aliphatic and aromatic primary amines using methanol as the methylating agent. Iridium complexes bearing an N-heterocyclic carbene (NHC) ligand exhibited high catalytic performance for this type of transformation. For aliphatic amines, selective N,N-dimethylation was achieved at low temperatures (50–90 °C). For aromatic amines, selective N-monomethylation and selective N,N-dimethylation were accomplished by simply changing the reaction conditions (presence or absence of a base with an appropriate catalyst). These findings can be used to develop methods for synthesizing useful amine compounds having N-methyl or N,N-dimethyl moieties.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610252.
- Supporting Information (PDF)
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There are many precedent reports for the N-alkylation of amines with alcohols (not using MeOH) catalyzed by NHC complexes of transition metals. For example:
UV-promoted heterogeneous catalytic system for the N,N-dimethylation of primary amines has been also reported: