Palladium-catalyzed carbonylation of halo arene-cis-dihydrodiols to the corresponding carboxylates. Access to compounds unavailable by toluene dioxygenase-mediated dihydroxylation of the corresponding benzoate estersThe authors wish to dedicate this paper to the memory of David Gibson (deceased July 24, 2014) and in recognition of his lifetime contributions to the field of biocatalysis.Electronic supplementary information (ESI) available. See DOI: 10.1039/c4ob01417k

A series of arene- cis -dihydrodiol carboxylates was prepared by palladium-catalyzed carbonylation of (1 S , 2 S-cis )-3-iodo-3,5-cyclohexadiene-1,2-diol, which is obtained in high titers by enzymatic dihydroxylation of iodobenzene. Both the free diol and the corresponding acetonide were subjected to this protocol to produce various arene- cis -dihydrodiol carboxylates that are unavailable by fermentation of the corresponding benzoates or are produced in low yields. The comparison of yields obtained from fermentation versus carbonylation was made for all compounds investigated. Experimental and spectral data are provided for all new compounds. Compounds of high synthetic value were produced in a much more efficient manner than was previously possible through fermentation.