Biotransformation of ent-13-epi-manoyl oxides difunctionalized at C-3 and C-12 by filamentous fungi.
Biotransformation of ent-3beta,12alpha-dihydroxy-13-epi-manoyl oxide with Fusarium moniliforme gave the regioselective oxidation of the hydroxyl group at C-3 and the ent-7beta-hydroxylation. The action of Gliocladium roseum in the 3,12-diketoderivative originated monohydroxylations at C-1 and C-7, both by the ent-beta face, while Rhizopus nigricans produced hydroxylation at C-7 or C-18, epoxidation of the double bond, reduction of the keto group at C-3, and combined actions as biohydroxylation at C-2/epoxidation of the double bond and hydroxylation at C-7/reduction of the keto group at C-3. In the ent-3-hydroxy-12-keto epimers, G. roseum originated monohydroxylations at C-1 and C-7 and R. nigricans originated the oxidation at C-3 as a major transformation, epoxidation of double bond and hydroxylation at C-2. Finally, in the ent-3beta-hydroxy epimer R. nigricans also originated minor hydroxylations at C-1, C-6, C-7 and C-20 and F. moniliforme produced an hydroxylation at C-7 and a dihydroxylation at C-7/C-11.
García-Granados
Andrés
A
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Granada, E-18071, Granada, Spain. agarcia@ugr.es
Fernández
Antonia
A
Gutiérrez
María C
MC
Martínez
Antonio
A
Quirós
Raquel
R
Rivas
Francisco
F
Arias
José M
JM
D001711:Biotransformation; D004852:Epoxy Compounds / Q000737:chemistry; D005670:Fusarium / Q000378:metabolism*; D020462:Gliocladium / Q000378:metabolism*; D006900:Hydroxylation; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D010084:Oxidation-Reduction; D012233:Rhizopus / Q000378:metabolism*; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry* / Q000378:metabolism*
D004852:Epoxy Compounds; D013729:Terpenes; C423905:ent-13-epi-manoyl oxide