Journal of the American Chemical Society · 2014 · 215 citations · 47 references
Natural SciencesChemistryCatalysisInorganic ChemistryOrganic ChemistryCarbonyl ChemistryCatalyst PreparationCatalytic MechanismsCovalent CatalysisGreen CatalysisIndustrial CatalysisAmine FunctionalizationC - H Bond FunctionalizationCarbon DioxideCarbon Dioxide ReductionCarbon Dioxide Reduction CatalysisFormaldehydeHydrolysisMild Reaction Conditions
Functionalization of CO2 is a challenging goal and precedents exist for the generation of HCOOH, CO, CH3OH, and CH4 in mild conditions. In this series, CH2O, a very reactive molecule, remains an elementary C1 building block to be observed. Herein we report the direct observation of free formaldehyde from the borane reduction of CO2 catalyzed by a polyhydride ruthenium complex. Guided by mechanistic studies, we disclose the selective trapping of formaldehyde by in situ condensation with a primary amine into the corresponding imine in very mild conditions. Subsequent hydrolysis into amine and a formalin solution demonstrates for the first time that CO2 can be used as a C1 feedstock to produce formaldehyde.
47