Methylformate as replacement of syngas in one-pot catalytic synthesis of amines from olefins

Abstract

A new general approach for the one-pot hydroaminomethylation of olefins using methylformate as formylating agent instead of synthesis gas (syngas) has been proposed. Herein we report that a Ru–Rh catalytic system demonstrates high activity in a tandem conversion of a series of n-alkenes into amines using methylformate with yields 58–92% (6 h). The selectivity for the normal amine reached 96% with catalysis by the Ru carbonyl complex Ru₃(CO)₁₂, with an overall yield of 55% with respect to amine in this instance. The addition of the Rh complex to Ru catalytic system, sharply increased the hydroaminomethylation rate of both the terminal and internal alkenes and increased the yield of amines to 82–93% (6–12 h).