Herbert C. Murray

Microbial oxygenation of dialkylbenzenes (I)

Abstract The use of the microorganism Sporotrichum sulfurescens (ATCC 7159) to oxygenate organic molecules has been extended to several dialkylbenzenes. Oxygenation of 1,4-di- t -butylbenzene ( 1 ) gave 4- t -butyl(1-hydroxy-2-methyl)isopropylbenzene ( 2 ) and 1,4-di-(1-hydroxy-2-methyl)isopropylbenzene ( 3 ); of 1,4-diisopropylbenzene ( 4 ) gave ( R,R )-1,4-di-(1-hydroxy)isopropylbenzene ( 5 ); of 1,3-diisopropylbenzene ( 6 ) gave 1,3-di-(2-hydroxy)isopropylbenzene ( 7 ), 3-(1-hydroxy)isopropyl-(2-hydroxy)isopropylbenzene ( 8 ), and 1,3-di-(1-hydroxy)isopropylbenzene ( 9 ); and of p -isobutylisopropylbenzene ( 20 ) gave 1-( p -2-hydroxyisopropylphenyl)-2-methylpropan-2-ol ( 15 ) and 1-( p -1-hydroxyisopropylphenyl)-2-methylpropan-2-ol ( 16 ). Monohydroxydialkylbenzenes also served as useful substrates in this reaction as suggested by the fact that 2 is an intermediate in the formation of 3 from 1 . Oxygenation of 1-( p -isopropylphenyl)-2-methylpropan-2-ol ( 14 ), conveniently prepared from 2-( p -isopropylphenyl)propene ( 12 ) via oxygenative isomerization with thallium trinitrate to 13 followed by addition of methyl magnesium bromide, gave 15 and 16 . Oxygenation of 2-( p -isobutylphenyl)propan-2-ol ( 18 ) gave 15 , 2-( p -isobutylphenyl)-propan-1,2-diol ( 21 ), and 1-( p -2-hydroxyisopropylphenyl)-2-methylpropan-3-ol ( 22 ). Compound 16 , obtained from substrate 14 , was converted to (2 R )-2-[4-(2-hydroxy-2-methylpropyl)phenyl]propionic acid ( 11 ), the enantiomer of a metabolite of the antiinflammatory agent, 2-(4- i -butyl)phenylpropionic acid ( 10 ).

Microbial hydroxylation of 1,2-(α-oxotetramethylene)ferrocene

Hydroxylation of α-oxo-1,2-tetramethylene-ferrocene with the mould Sporotrichum sulfurescens gave exo-6-hydroxyferroceno[1,2]cyclohex-1-en-3-one, demon-strating the capacity for oxygenation of hydrocarbons by enzymic systems in the presence of the ferrocene moiety.