Steroid compounds with a 6,19-oxirane bridge possess interesting biological activities including anticonvulsant and analgesic properties, bacteriostatic activity against Gram-positive bacteria and selective anti-glucocorticoid action, while lacking mineralocorticoid and progestagen activity. The study aimed to obtain new derivatives of 3β-acetyloxy-5α-chloro-6,19-oxidoandrostan-17-one by microbial transformation. Twelve filamentous fungal strains were used as catalysts, including entomopathogenic strains with specific activity in the transformation of steroid compounds. All selected strains were characterised by high biotransformation capacity for steroid compounds. However, high substrate conversions were obtained in the cultures of 8 strains: Beauveria bassiana KCh BBT, Beauveria caledonica KCh J3.4, Penicillium commune KCh W7, Penicillium chrysogenum KCh S4, Mucor hiemalis KCh W2, Fusarium acuminatum KCh S1, Trichoderma atroviride KCh TRW and Isaria farinosa KCh KW1.1. Based on gas chromatography (GC) and nuclear magnetic resonance (NMR) analyses, it was found that almost all strains hydrolysed the ester bond of the acetyl group. The strain M. hiemalis KCh W2 reduced the carbonyl group additionally. From the P. commune KCh W7 and P. chrysogenum KCh S4 strain cultures a product of D-ring Baeyer–Villiger oxidation was isolated, whereas from the culture of B. bassiana KCh BBT a product of hydroxylation at the 11α position and oxidation of the D ring was obtained. Three 11α-hydroxy derivatives were obtained in the culture of I. farinosa KCh KW1.1: 3β,11α-dihydroxy-5α-chloro-6,19-oxidoandrostan-17-one, 3β,11α,19-trihydroxy-5α-chloro-6,19-oxidoandrostan-17-one and 3β,11α-dihydroxy-5α-chloro-6,19-oxidoandrostan-17,19-dione. They are a result of consecutive reactions of hydrolysis of the acetyl group at C-3, 11α- hydroxylation, then hydroxylation at C-19 and its further oxidation to lactone. As a result of the biotransformations, seven steroid derivatives, not previously described in the literature, were obtained: 3β-hydroxy-5α-chloro-6,19-oxidoandrostan-17-one, 3β,17α-dihydroxy-5α-chloro-6,19-oxidoandrostane, 3β-hydroxy-5α-chloro-17α-oxa-D-homo-6,19-oxidoandrostan-17-one, 3β,11α-dihydroxy-5α-chloro-17α-oxa-D-homo-6,19-oxidoandrostan-17-one and the three above–mentioned 11α-hydroxy derivatives. This study will allow a better understanding and characterisation of the catalytic abilities of individual microorganisms, which is crucial for more accurate planning of experiments and achieving more predictable results.

中文翻译：

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通过在环境丝状真菌培养物中进行生物转化获得的新的6,19-氧化雄激素衍生物

具有6,19-环氧乙烷桥的类固醇化合物具有有趣的生物学活性，包括抗惊厥和止痛特性，对革兰氏阳性细菌的抑菌活性和选择性的抗糖皮质激素作用，而缺乏盐皮质激素和孕激素活性。该研究旨在通过微生物转化获得3β-乙酰氧基-5α-氯-6,19-氧化雄甾烷17-one的新衍生物。使用十二种丝状真菌菌株作为催化剂，包括在类固醇化合物转化中具有特定活性的昆虫致病菌株。所有选择的菌株均以对类固醇化合物的高生物转化能力为特征。但是，在8个菌株的培养物中获得了较高的底物转化率：球孢白僵菌KCh BBT，球孢白僵菌KCh J3.4，青霉公社KCh W7，产黄青霉菌KCh S4，毛霉菌KCh W2，尖孢镰刀菌KCh S1，木霉木霉菌KCh TRW和粉刺木瓜KCh KW1.1。基于气相色谱（GC）和核磁共振（NMR）分析，发现几乎所有菌株都水解了乙酰基的酯键。hiemalis KCh W2菌株另外还原了羰基。从P. com.une的KCh W7和P. chrysogenum KCh S4菌株培养物中分离出D环Baeyer-Villiger氧化产物，而从B. bassiana KCh BBT的培养物中分离出11α位置的羟基化产物并氧化。获得D环。在粉far ICh.KCh KW1.1的培养物中获得了三种11α-羟基衍生物：3β，11α-二羟基-5α-氯-6,19-氧化雄甾酮17-一，3β，11α，19-三羟基-5α-氯-6,19-oxidandandrostan-17-one和3β，11α-二羟基-5α-氯-6,19-氧化雄酮-17,19-二酮。它们是在C-3处乙酰基水解，11α-羟基化，然后在C-19处羟基化以及其进一步氧化为内酯的连续反应的结果。生物转化的结果是，获得了七种以前未在文献中描述的类固醇衍生物：3β-羟基-5α-氯-6,19-氧化雄酮-17-一，3β，17α-二羟基-5α-氯-6 ，19-氧化雄甾烷，3β-羟基-5α-氯-17α-oxa-D-homo-6,19-氧化雄甾烷-17-one，3β，11α-二羟基-5α-氯-17α-oxa-D-homo-6 ，19-oxidandostanstan-17-one和上述三个11α-羟基衍生物。这项研究将使人们更好地了解和表征单个微生物的催化能力，这对于更准确地计划实验和获得更可预测的结果至关重要。