Oxalate from Air: In light of increasing concerns about the consequences of excessive atmospheric carbon dioxide, there is demand for methods to use carbon dioxide in the preparation of more elaborate compounds. Though reactions with hydroxide salts to form carbonates tend to proceed fairly cleanly, reductive processes to form carboxylic acids, esters, and alcohols are often rather unselective.
Angamuthu
et al. (p. 313 ; see the news story by Service ) discovered that a copper complex exhibited remarkable selectivity in reductively coupling carbon dioxide to form oxalate through coordinative electron transfer, even in the presence of excess oxygen, normally a much more potent electron acceptor. Precipitation of the oxalate as a lithium salt and electrochemical re-reduction of the copper produced a preliminary catalytic cycle, demonstrated through six turnovers.
13 December 2011 in Journal of the American Chemical Society
Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub‐stoichiometric amounts of KOtBu base.
13 June 2014 in Journal of the American Chemical Society