Efficient and Selective N-Methylation of Nitroarenes under Mild Reaction Conditions

Elena Pedrajas, Iván Sorribes, Eva Guillamón, Kathrin Junge, Matthias Beller, Rosa Llusar

Research output: Contribution to journalArticlepeer-review

32 Scopus citations

Abstract

Herein, we report a straightforward protocol for the preparation of N,N-dimethylated amines from readily available nitro starting materials using formic acid as a renewable C1 source and silanes as reducing agents. This tandem process is efficiently accomplished in the presence of a cubane-type Mo3PtS4 catalyst. For the preparation of the novel [Mo3Pt(PPh3)S4Cl3(dmen)3]+ (3+) (dmen: N,N′-dimethylethylenediamine) compound we have followed a [3+1] building block strategy starting from the trinuclear [Mo3S4Cl3(dmen)3]+ (1+) and Pt(PPh3)4 (2) complexes. The heterobimetallic 3+ cation preserves the main structural features of its 1+ cluster precursor. Interestingly, this catalytic protocol operates at room temperature with high chemoselectivity when the 3+ catalyst co-exists with its trinuclear 1+ precursor. N-heterocyclic arenes, double bonds, ketones, cyanides and ester functional groups are well retained after N-methylation of the corresponding functionalized nitroarenes. In addition, benzylic-type as well as aliphatic nitro compounds can also be methylated following this protocol.

Original languageEnglish
Pages (from-to)13205-13212
Number of pages8
JournalChemistry - A European Journal
Volume23
Issue number53
DOIs
StatePublished - 21 Sep 2017
Externally publishedYes

Keywords

  • cubane-type clusters
  • formic acid
  • methylation
  • nitroarenes
  • tandem catalysis

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