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Convenient Reductive Methylation of Amines with Carbonates at Room Temperature
Author(s) -
Li Yuehui,
Sorribes Iván,
Vicent Cristian,
Junge Kathrin,
Beller Matthias
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201502917
Subject(s) - chemoselectivity , formic acid , methanol , chemistry , catalysis , formaldehyde , methylation , substrate (aquarium) , combinatorial chemistry , organic chemistry , biochemistry , oceanography , gene , geology
Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt‐based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ‐formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry.