Synthesis and Reactions of Enantiopure Substituted Benzene cis-Hexahydro-1,2-diols.

D. R. BOYD, N. D. SHARMA, M. V. BERBERIAN, K. S. DUNNE, C. HARDACRE, M. KAIK, B. KELLY, J. F. MALONE, S. T. MCGREGOR, P. STEVENSON.

ADVANCED SYNTHESIS & CATALYSIS (PRINT)

WILEY-V C H VERLAG GMBH

Año: 2010 vol. 352 p. 855 - 868

1615-4150

Enantiopure-dihydro-1,2-diol metabolites, obtained from toluene dioxygenase-catalysed -dihydroxylation of six monosubstituted benzene substrates, have been converted to their corresponding -hexahydro-1,2-diol derivatives by catalytic hydrogenation via their cis-tetrahydro-1,2-diol intermediates. Optimal reaction conditions for total catalytic hydrogenation of the cis-dihydro-1,2-diols have been established using six heterogeneous catalysts. The relative and absolute configurations of the resulting benzene cis-hexahydro-1,2-diol products have been unequivocally established by X-ray crystallography and NMR spectroscopy. Methods have been developed to obtain enantiopure cis-hexahydro-1,2-diol diastereoisomers, to desymmetrise a meso-cis-hexahydro-1,2-diol and to synthesise 2-substituted cyclohexanols. The potential of these enantiopure cyclohexanols as chiral reagents was briefly evaluated through their application in the synthesis of two enantiomerically enriched phosphine oxides from the corresponding racemic phosphine precursors.