Ruthenium carbonyl-complex catalyzed hydroaminomethylation of olefins with carbon dioxide and amines

Use of carbon dioxide as a reactant instead of toxic carbon monoxide in the hydroaminomethylation reaction sequence is demonstrated for the first time. The present Ru₃(CO)₁₂-catalyzed one-pot protocol includes reverse-water–gas-shift (RWGS) reaction, hydroformylation reaction and reductive amination which finally leads to secondary and tertiary amine. The influence of various reaction parameters including the effects of catalytic promotors and phase-transfer-catalysts has been investigated. Finally, an optimum reaction conditions were found by suppressing the major side products to have a variety of amines in excellent yields (up to 98%).