A study of some molecularly imprinted polymers as protic catalysts for the isomerisation of α-pinene oxide to trans-carveol

A range of acidic Molecularly Imprinted Polymers (MIPs) were synthesised using the imprint molecule trans-carvyl amine as a transition state analogue for the selective isomerisation of alpha-pinene oxide to trans-carveol. The amine functionality of the imprint molecule was used to selectively position a sulfonic acid group in the MIP binding pocket utilising 4-styrene sulfonic acid as the functional monomer. Co-polymerisation with varying ratios of styrene and divinylbenzene afforded a range of MIPs which were tested for their ability to effect selective formation of trans-carveol from alpha-pinene oxide. Although successful imprinting was demonstrated in binding studies, it was shown that solvent effects were dominant in effecting selective formation of trans-carveol. Using DMF as solvent, up to 70% of the products from acid catalysed isomerisation of alpha-pinene oxide with the polystyrene MIPs were obtained via the necessary para menthyl tertiary carbocation, and industrially important trans-carveol was obtained in 45% yield. (C) 2004 Elsevier Ltd. All rights reserved.