丝状真菌对在C-3和C-12位双官能化的对映-13-表-半日花烷氧化物的生物转化。

Biotransformation of ent-13-epi-manoyl oxides difunctionalized at C-3 and C-12 by filamentous fungi.

作者信息

García-Granados Andrés, Fernández Antonia, Gutiérrez María C, Martínez Antonio, Quirós Raquel, Rivas Francisco, Arias José M

机构信息

Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Granada, E-18071, Granada, Spain.

出版信息

Phytochemistry. 2004 Jan;65(1):107-15. doi: 10.1016/j.phytochem.2003.09.017.

DOI:10.1016/j.phytochem.2003.09.017

PMID:14697276

Abstract

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.

摘要

镰刀菌对 ent-3β,12α-二羟基-13-表-莫尼内酯进行生物转化，使 C-3 位羟基发生区域选择性氧化，并生成 ent-7β-羟基化产物。粉红粘帚霉对 3,12-二酮衍生物的作用导致在 C-1 和 C-7 位均发生单羟基化，且均从 ent-β 面进行，而黑根霉则使 C-7 或 C-18 位发生羟基化、双键环氧化、C-3 位酮基还原，以及 C-2 位生物羟基化/双键环氧化和 C-7 位羟基化/C-3 位酮基还原的联合作用。在 ent-3-羟基-12-酮差向异构体中，粉红粘帚霉使 C-1 和 C-7 位发生单羟基化，黑根霉则以 C-3 位氧化作为主要转化反应，同时伴有双键环氧化和 C-2 位羟基化。最后，在 ent-3β-羟基差向异构体中，黑根霉还使 C-1、C-6、C-7 和 C-20 位发生少量羟基化，镰刀菌则使 C-7 位发生羟基化以及 C-7/C-11 位发生二羟基化。