The hydrocarbalkoxylation of propene promoted by a [PdCl2(PPh3)2]-PPh3 catalyst precursor occurs (at 100-110°, PCO 10-100 atm) with high selectivity towards the branched isomer when a solvent is added to the alkanol. The selectivity increases on increasing the solvent/alkanol ratio, or on increasing PCO, or in the presence of LiCl, and decreases upon increasing the concn. of PPh3. The results are discussed in terms of steric effects. The yield decreases on increasing the solvent/alkanol ratio, or on increasing the concn. of PPh3, or upon decreasing PCO. Primary or secondary alkanols show comparable reactivity; tertiary alkanols give poor yields. The yield can be improved in the presence of mol. H without affecting the regioselectivity.
Metals in organic syntheses. VI. The solvent effect on the hydrocarbalkoxylation of propene promoted by abis(triphenylphosphine)palladium dichloride-triphenylphosphine catalyst precursor
TONIOLO, Luigi
1981-01-01
Abstract
The hydrocarbalkoxylation of propene promoted by a [PdCl2(PPh3)2]-PPh3 catalyst precursor occurs (at 100-110°, PCO 10-100 atm) with high selectivity towards the branched isomer when a solvent is added to the alkanol. The selectivity increases on increasing the solvent/alkanol ratio, or on increasing PCO, or in the presence of LiCl, and decreases upon increasing the concn. of PPh3. The results are discussed in terms of steric effects. The yield decreases on increasing the solvent/alkanol ratio, or on increasing the concn. of PPh3, or upon decreasing PCO. Primary or secondary alkanols show comparable reactivity; tertiary alkanols give poor yields. The yield can be improved in the presence of mol. H without affecting the regioselectivity.
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