|Budget Amount *help
¥1,800,000 (Direct Cost : ¥1,800,000)
Fiscal Year 1999 : ¥500,000 (Direct Cost : ¥500,000)
Fiscal Year 1998 : ¥1,300,000 (Direct Cost : ¥1,300,000)
In this study, the aim is development of 5 components coupling reaction. That is, in the presence of alkyl halides and tricarbonylnitrosylferrate, acylmetallation of 1,3-butaienes or 1,2-dienes was discussed and the carbonyl insertion reaction of the resulting iron complexes with 1,2-bis(diphenylphosphino)ethane (DPPE) following the alcoholysis with ethanol was discussed. In the result, the coupling reaction of 5 components of 1,2-dienes or 1,3-butadienes, two molecules of carbon monoxide from tricarbonylnitrosylferrate, alkyl halides, and ethanol completes stereo- and regioselectively.
In the presence of tetrabutylammmonium tricarbonylnitrosylferrate (TBAFe), 1,2-dienes (allenes) and alkyl halides reacted to give (η^3-2-acylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of allenes in good yields.
In the presence of TBAFe, 1,3-butadienes and alky1 halides reacted to give (η^3-1-acylmethylally1) dicarbonylnitrosyliron complexes accompanied with acylmetallation of 1,3-butadienes in good yields. The resulting iron complexes reacted with DPPE at the less hindered site of the allylic ligand to give ε-acy1-β, γ-unsaturated acyliron complexes. In succession, the alcoholysis of the acyliron complexes with ethanol gave the corresponding ε-acy1-β, γ-unsaturated carboxylic esters. In a similar manner, (η^3-2-acylally1) dicarbony1-nitrosyliron complexes obtained from 1,2-dienes (allenes) and alky1 halides with TBAFe gave the β-acy1-β, γ-unsaturated acyliron complexes followed by alcoholysis with ethanol to give the β-acy1-β, γ-unsaturated carboxylic esters.