Journal of the Chemical Society, Dalton Transactions p. 1793 - 1800 (1996)
Update date:2022-08-17
Topics:
Simpson, Michael C.
Currie, Alan W. S.
Andersen, Jo-Ann M.
Cole-Hamilton, David J.
Green, Michael J.
The hydrocarbonylation of prop-2-ene-1-ol catalysed by [Rh2(O2CMe)4]-PEt3, which gives [RhH(CO)(PEt3)2] as the active species, has been found to produce predominantly butane-1,4-diol and 2-methylpropan-1-ol with small amounts of 2-methylpropane-1,3-diol and propan-1-ol. Neither 2-methylprop-2-enal nor 2-methylprop-2-en-1-ol are intermediates in the production of 2-methylpropan-1-ol. By carrying out the reaction under a variety of reaction conditions and by using deuterium-labelling studies it was possible to formulate a mechanism for the production of 2-methylpropan-1-ol which involves formation of the vinyl alcohol, 2-methylprop-1-en-1-ol, as the primary product followed by tautomerism and hydrogenation, provided that at least two PEt3 groups are co-ordinated to the rhodium. A dehydration is proposed to occur during the catalytic cycle from a cationic hydroxycarbene intermediate. Using propenyl ethers as substrates similar products are obtained presumably via loss of alcohol rather than dehydration. If less than two PEt3 groups are co-ordinated to rhodium the major branched-chain product from prop-2-en-1-ol is 2-methylpropane-1,3-diol. This is interpreted as indicating that protonation of the acyl intermediate and dehydration of the hydroxycarbene do not occur because of the lower electron density on the acyl O atom.
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