| Affiliation: | 1. Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588 Japan Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502 Japan;2. Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo, 184-8588 Japan |
| Abstract: | A novel route to synthesize 1,4-dicarbonyl compounds is described. α,α-Dibromoketones generate zinc enolates through a diethylzinc-mediated halogen-metal exchange and react with α-bromocarbonyl compounds to furnish 1,4-dicarbonyl compounds via a second generation of zinc enolates. This cross-coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α-dibromoketones in the presence of α-bromocarbonyl compounds. Chiral 1,4-dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes using a chiral secondary amine catalyst and a subsequent cross-coupling reaction between the resulting chiral α-bromoaldehydes and α,α-dibromoacetophenones. |
