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

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 Mo3 PtS4 catalyst. For the preparation of the novel [Mo3 Pt(PPh3 )S4 Cl3 (dmen)3 ]+ (3+ ) (dmen: N,N'-dimethylethylenediamine) compound we have followed a [3+1] building block strategy starting from the trinuclear [Mo3 S4 Cl3 (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.