Iridium-Catalyzed Hydroalkylation of Aliphatic Alkenes with Β-Ketoesters: Formal Hydroalkylation with Methyl Ketones.

Transition-metal-catalyzed hydroalkylation of alkenes with 1,3-dicarbonyl compounds is a useful reaction to construct a C-C bond under neutral reaction conditions in a highly atom-economical manner. We found that hydroalkylation of aliphatic alkenes with beta-ketoesters proceeded with the use of a cationic iridium complex and bidentate phosphine ligand to give selectively branched alpha-substituted beta-ketoesters in high yields. The obtained hydroalkylated compounds can be converted to beta-substituted ketones through one-pot Krapcho dealkoxycarbonylation.