Electroorganic Chemistry. 140. Electroreductively Intra- and Intermolecular Couplings of Ketones with Nitriles

Article abstract of DOI:10.1021/jo00052a036

Electroreduction of γ- and δ-cyano ketones in i-PrOH with Sn cathode gave α-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products.Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of γ- and δ-cyano ketones in one of the key steps.Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product.The product obtained by the electroreductive intermolecular coupling of (+)-dihydrocarvone with acetonitrile has been found to be the precursor of an effective chiral ligand for the enantioselective addition of diethylzinc to aldehydes.