3β-hydroxy-17a-oxa-D-homo-5α-androstan-17-one | 2061-71-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: 3β-hydroxy-17a-oxa-D-homo-5α-androstan-17-one
• 英文别名: Isoandrololactone；(4aS,4bR,6aS,8S,10aS,10bS,12aS)-8-hydroxy-10a,12a-dimethyl-3,4,4a,4b,5,6,6a,7,8,9,10,10b,11,12-tetradecahydronaphtho[2,1-f]chromen-2-one
• CAS: 2061-71-4
• 化学式: C₁₉H₃₀O₃
• 分子量: 306.445
• InChiKey: SZKJPNYYJWKGMH-BECBKZTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3β-hydroxy-17a-oxa-D-homo-5α-androstan-17-one 在 二异丁基氢化铝 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 8.5h， 生成 (4aS,4bR,6aS,8S,10aS,10bS,12aS)-8-(1-Ethoxy-ethoxy)-10a,12a-dimethyl-hexadecahydro-1-oxa-chrysen-2-ol
  参考文献：
  名称：

  Transformation of epiandrosterone into 3-oxa-, 3-thia-, 3-selena-, and 3-aza-17-oxaandrostanes of the 5α series based on β-scission of alkoxyl radicals

  摘要：

  3-beta-Hydroxy-5-alpha-androstan-17-one was transformed into 17-oxa-5-alpha-androstan-3-beta-ol in five steps involving conversion of the 17-ketone via the corresponding lactol to its hypoiodite and thence a regioselective beta-scission under irradiation to give ring D seco iodoformate, from which the 17-oxasteroids were derived. Four bisheterosteroids 3,17-dioxa-5-alpha-androstane, 3-thia-17-oxa-5-alpha-androstane, 3-aza-17-oxa-5-alpha-androstane, and 3-selena-17-oxa-5-alpha-androstane) were synthesized from 17-oxa-5-alpha-androstan-3-beta-ol via 5, 8, 8, and 9 steps, respectively, involving a second regioselective beta-scission of an alkoxyl radical as the key step.

  DOI：

  10.1016/0039-128x(90)90059-k
• 作为产物：
  描述：

  3β-acetoxy-17a-oxa-D-homo-5α-androstan-17-one 在 水 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 生成 3β-hydroxy-17a-oxa-D-homo-5α-androstan-17-one
  参考文献：
  名称：

  Cephalosporium aphidicola对甾体环D内酯的羟基化作用

  摘要：

  摘要 Cephalosporium aphidicola 的 17a-oxa-d-homo-5α-androstane-3,17-dione、3β-醇和 13α-甲基类似物的微生物羟基化主要发生在 C-7α生物。

  DOI：

  10.1016/s0031-9422(98)00286-6

文献信息

• Regioselective Baeyer-Villiger Oxidation of Steroidal Ketones to Lactones Using BF₃/H₂O₂
  作者：Alexey I. Ilovaisky、Valentina M. Merkulova、Vera A. Vil'、Elena I. Chernoburova、Marina A. Shchetinina、Sergey D. Loguzov、Andrey S. Dmitrenok、Igor V. Zavarzin、Alexander O. Terent'ev

  DOI：10.1002/ejoc.201901701

  日期：2020.1.23

  The traditional system for peroxide synthesis – BF3·Et2O/H2O2 leads to regioselective Baeyer–Villiger oxidation of steroidal ketones to produce the corresponding lactones.

  传统的过氧化物合成系统-BF 3 · Et 2 O / H 2 O 2导致甾体酮的区域选择性Baeyer-Villiger氧化，生成相应的内酯。
• Baeyer–Villiger oxidation of some steroids by Aspergillus tamarii MRC 72400
  作者：Kudret Yildirim、Ahmet Uzuner、Emine Yasemin Gulcuoglu

  DOI：10.1135/cccc2011008

  日期：——

  Biotransformations of epiandrosterone (1), dehydroepiandrosterone (2), testosterone (3), progesterone (4) and pregnenolone (5) byAspergillus tamariiMRC 72400 for 5 days have been reported and the results of these incubations have been compared with previously published data obtained withAspergillus tamariiQM 1223.A. tamariiMRC 72400 showed higher Bayer–Villiger monooxygenase activities thanA. tamariiQM 1223 did. Apart from pregnenolone (5),A. tamariiMRC 72400 metabolized these steroids in different ways. Incubation of epiandrosterone (1) afforded 3β,11β-dihydroxy-5α-androstan-17-one (6) (3%) and 3β-hydroxy-17a-oxa-D-homo-5α-androstan-17-one (7) (9.5%). Incubation of dehydroepiandrosterone (2) afforded 3β-hydroxy-17a-oxa-D-homoandrost-5-en-17-one (8) (28%), testolactone (9) (6%), 3β,7β-dihydroxyandrost-5-en-17-one (10) (13%) and 3β,7α-dihydroxy- androst-5-en-17-one (11) (24%). Incubation of testosterone (3) afforded testolactone (9) (58%). Incubation of progesterone (4) also afforded testolactone (9), however in higher yield (86%). Incubation of pregnenolone (5) afforded 3β-hydroxy-17a-oxa-D-homoandrost-5-en-17-one (8) (25%) and testolactone (9) (27%).

  对于Epiandrosterone（1），去氢表雄酮（2），睾酮（3），孕酮（4）和孕酮醇（5）在5天内由Aspergillus tamarii MRC 72400进行的生物转化已经报道，并将这些培养结果与之前使用Aspergillus tamarii QM 1223获得的数据进行了比较。A. tamarii MRC 72400显示出比A. tamarii QM 1223更高的Bayer-Villiger单氧酶活性。除了孕酮醇（5）外，A. tamarii MRC 72400以不同方式代谢这些类固醇。Epiandrosterone（1）的培养产生了3β，11β-二羟基-5α-雄烷-17-酮（6）（3％）和3β-羟基-17a-氧杂-D-同型-5α-雄烷-17-酮（7）（9.5％）。去氢表雄酮（2）的培养产生了3β-羟基-17a-氧杂-D-同型雄烷-5-烯-17-酮（8）（28％），睾酮内酯（9）（6％），3β，7β-二羟基雄烷-5-烯-17-酮（10）（13％）和3β，7α-二羟基-雄烷-5-烯-17-酮（11）（24％）。睾酮（3）的培养产生了睾酮内酯（9）（58％）。孕酮（4）的培养也产生了睾酮内酯（9），但产率更高（86％）。孕酮醇（5）的培养产生了3β-羟基-17a-氧杂-D-同型雄烷-5-烯-17-酮（8）（25％）和睾酮内酯（9）（27％）。
• Expedited Baeyer–Villiger oxidation of steroidal ketones by microwave irradiation
  作者：Juri Moni Borah、Pritish Chowdhury

  DOI：10.1016/j.steroids.2011.06.014

  日期：2011.11

  compounds. Considering the remarkable application of Baeyer-Villiger (BV) reaction in the synthesis of natural products and steroid-peptide conjugates, we report here some of our findings of BV oxidation of carbonyl compounds with special reference to steroidal ketones under MW irradiation justifying its accelerating effect.

  微波（MW）辅助反应目前在有机化合物的合成中具有相当重要的意义。考虑到Baeyer-Villiger（BV）反应在天然产物和类固醇-肽共轭物的合成中的显着应用，我们在此报告了MW辐射下羰基化合物BV氧化的一些发现，特别是甾体酮，证明了其加速作用。
• Epiandrosterone- and Dehydroepiandrosterone-3β-alkanesulfonates as Inhibitors of Mouse Glucose-6-phosphate Dehydrogenase Activity
  作者：Magid Abou-Gharbia、Elaine N. Cheeseman、Laura Pashko、Arthur Schwartz、Daniel Swern

  DOI：10.1002/jps.2600731140

  日期：1984.11

  prepared in 54-95% yield via the reaction of long chain alkanesulfonyl chlorides with the corresponding dehydroepiandrosterone, and epiandrosterone analogues. These compounds inhibit mouse glucose-6-phosphate dehydrogenase activity.

  通过长链链烷磺酰氯与相应的脱氢表雄酮和表雄甾酮类似物的反应，以54-95％的收率制备了3种脱氢表雄酮，16种α-溴脱氢表雄酮，表雄甾酮和16种α-溴表雄酮的β-烷磺酸盐。这些化合物抑制小鼠葡萄糖6-磷酸脱氢酶活性。
• Microbial Modifications of Androstane and Androstene Steroids by Penicillium vinaceum
  作者：Anna Panek、Paulina Łyczko、Alina Świzdor

  DOI：10.3390/molecules25184226

  日期：——

  of steroid compounds is a promising, environmentally friendly route to new pharmaceuticals and hormones. One of the reaction types common in the metabolic fate of steroids is Baeyer-Villiger oxidation, which in the case of cyclic ketones, such as steroids, leads to lactones. Fungal enzymes catalyzing this reaction, Baeyer-Villiger monooxygenases (BVMOs), have been shown to possess broad substrate scope

  类固醇化合物的生物转化是一种有前途的、环境友好的新药物和激素途径。类固醇代谢过程中常见的一种反应类型是拜尔-维利格氧化，在环酮（如类固醇）的情况下，会产生内酯。催化该反应的真菌酶 Baeyer-Villiger 单加氧酶 (BVMO) 已被证明具有广泛的底物范围、选择性和与化学氧化竞争的催化性能，并且更加环保。本研究涵盖了一系列雄甾烷类固醇（表雄酮和雄甾酮）和雄甾烯类固醇（黄体酮、孕烯醇酮、脱氢表雄酮、雄烯二酮、19-OH-雄烯二酮、睾酮、和 19-去甲睾酮）由丝状真菌 Penicillium v​​inaceum AM110 培养而成。通过 GC 监测转化，并在色谱和光谱数据的基础上鉴定所得产物。研究的真菌对底物进行有效的 Baeyer-Villiger 氧化。有趣的是，将 19-OH 基团引入雄烯二酮骨架对 BVMO 活性具有显着的抑制作用，因为 10 天的转化使 19-OH-雄烯二酮