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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
Autor*innen
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.
Weitere Informationen
Publikationsverlauf
Received: 25. Mai 2018
Accepted after revision: 25. Juli 2018
Publikationsdatum:
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) (opens in new window)
-
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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: