Synthesis of New Aliphatic Carbonyl Derivatives with Palladium (II) Catalyst

抄録

Bis-alkoxylcarbonylation of dicyclopentadiene (DCPD) with carbon monoxide and a variety of alcoholsin the presence of palladium (II) catalyst and copper (II) salt as reoxidant have been studied andtricyclo [5.2.1.0^{2, 6}] dec-3-ene-8, 9-diester (TCDE) and tricyclo [5.2.1.0^{2, 6}] dec-3-ene-8, 9-dicarboxylic anhydride (TCDA) successfully were obtained for the first time. It is found that the double bond in the norboranenering can selectively be diesterified without affecting double bond in the cyclopentene ring, to obtain TCDE in good yield. When lower alcohols such as methanol and n-butanol are used, TCDE is obtainable in a highyield, however, branched alcohols such as sec-butanol or cyclohexanol and higher alcohol such as n-decanol gave TCDE in a yield ranging from 66% to 61%. Tert-alcohols such as tert-butanol or tert-amyl alcohol gave TCDA exclusively. It is the first example showing the selectively directly diesterifying one of the double binds in the DCPD.