CARBON-MONOXIDE AS A BUILDING-BLOCK IN ORGANIC-SYNTHESIS .5. INVOLVEMENT OF PALLADIUM-HYDRIDE SPECIES IN CARBONYLATION REACTIONS OF MONOTERPENES - X-RAY CRYSTAL-STRUCTURE OF [PH3PCH2CH=CHPH]4[PDCL6]SNCL6]
R. Naigre et al., CARBON-MONOXIDE AS A BUILDING-BLOCK IN ORGANIC-SYNTHESIS .5. INVOLVEMENT OF PALLADIUM-HYDRIDE SPECIES IN CARBONYLATION REACTIONS OF MONOTERPENES - X-RAY CRYSTAL-STRUCTURE OF [PH3PCH2CH=CHPH]4[PDCL6]SNCL6], Journal of organometallic chemistry, 480(1-2), 1994, pp. 91-102
A palladium precursor and SnCl2 as cocatalyst were used under 4 MPa of
carbon monoxide for the catalytic alkoxycarbonylation of several mono
terpenes into C-11 esters. The active catalyst involves a palladium-hy
dride species whose formation was investigated. In the case of the mod
el substrate 3-phenylpropene, the source of the hydrido ligand was det
ermined to be the alkene itself. Allylic hydrogen abstraction seems to
be a general way to produce the active hydridopalladium species since
monoterpenes having labile allylic hydrogens were converted under exc
eptional mild conditions. An X-ray crystal structure analysis was carr
ied out on [(Ph3PCH2CH=CHPh)4(PdCl6)(SnCl6)].