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Synthesis and Reactions of Enantiopure Substituted Benzene cis ‐Hexahydro‐1,2‐diols
Author(s) -
Boyd D. R.,
Sharma N. D.,
Berberian M. V.,
Dunne K. S.,
Hardacre C.,
Kaik M.,
Kelly B.,
Malone J. F.,
McGregor S. T.,
Stevenson P. J.
Publication year - 2010
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200900818
Subject(s) - enantiopure drug , chemistry , diol , diastereomer , phosphine , benzene , cyclohexanol , catalysis , absolute configuration , organic chemistry , stereochemistry , medicinal chemistry , enantioselective synthesis
Enantiopure cis ‐dihydro‐1,2‐diol metabolites, obtained from toluene dioxygenase‐catalysed cis ‐dihydroxylation of six monosubstituted benzene substrates, have been converted to their corresponding cis ‐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.