syn-Benzene dioxides: chemoenzymatic synthesis from 2,3-cis-dihydrodiol derivatives of monosubstituted benzenes and their application in the synthesis of regioisomeric 1,2- and 3,4-cis-dihydrodiols and 1,4-dioxocins.
cis-2,3-Dihydrodiol metabolites of monosubstituted halobenzenes and toluene have been used as synthetic precursors of the corresponding 3,4-cis-dihydrodiols. Enantiopure syn-benzene dioxide intermediates were reduced to the 3,4-cis-dihydrodiols and thermally racemised via the corresponding 1,4-dioxocins. The syn-benzene dioxide-1,4-dioxocin valence tautomeric equilibrium ratio was found to be dependent on the substituent position. The methodology has also been applied to the synthesis of both enantiomers of the 1,2-(ipso)- and 3,4-cis-dihydrodiols of toluene. This chemoenzymatic approach thus makes available, for the first time, all three possible cis-dihydrodiol regioisomers of a monosubstituted benzene.
Boyd
Derek R
DR
School of Chemistry and Chemical Engineering, The Queen's University of Belfast, Belfast, UK BT9 5AG. dr.boyd@qub.ac.uk
Sharma
Narain D
ND
Llamas
Nuria M
NM
O'Dowd
Colin R
CR
Allen
Christopher C R
CC
D001555:Benzene Derivatives / Q000737:chemistry* / Q000378:metabolism*; D006900:Hydroxylation; D009281:Naphthalenes / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
D001555:Benzene Derivatives; D009281:Naphthalenes; C507866:trans-1,2-dihydro-1,2-naphthalenediol