Paper
Hydrocarbonylation of prop-2-en-1-ol to butane-1,4-diol and 2-methylpropan-1-ol catalysed by rhodium triethylphosphine complexes
Published 1996 · Michael C. Simpson, A. W. S. Currie, J. Andersen
Journal of The Chemical Society-dalton Transactions
12
Citations
0
Influential Citations
Abstract
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-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.
Hydrocarbonylation of prop-2-en-1-ol to butane-1,4-diol and 2-methylpropan-1-ol catalyzed by rhodium triethylphosphine complexes produces 2-methylpropan-1-ol, with 2-methyl
Sign up to use Study Snapshot
Consensus is limited without an account. Create an account or sign in to get more searches and use the Study Snapshot.
Full text analysis coming soon...