(3S,8R,9S,10R,13S,14S,17R)-3,17-二羟基-10,13-二甲基-1,2,3,4,7,8,9,11,12,14,15,17-十二氢环戊烯并[a]菲-16-酮 | 1159-66-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 中文名称: (3S,8R,9S,10R,13S,14S,17R)-3,17-二羟基-10,13-二甲基-1,2,3,4,7,8,9,11,12,14,15,17-十二氢环戊烯并[a]菲-16-酮
• 中文别名: (3S,8R,9S,10R,13S,14S,17R)-3,17-二羟基-10,13-二甲基-1,2,3,4,7,8,9,11,12,14,15,17-十二环戊醇[1]苯丙氨酸-16-酮
• 英文名称: 3β,17β-dihydroxyandrost-5-en-16-one
• 英文别名: 3beta,17beta-Dihydroxyandrost-5-en-16-one；3β,17β-dihydroxyandrost-5-ene-16-one；3β,17β-dihydroxy-androst-5-en-16-one；3β,17β-Dihydroxy-androst-5-en-16-on；3β.17β-Dihydroxy-androsten-(5)-on-(16)；16-Oxoandrostenediol；(3S,8R,9S,10R,13S,14S,17R)-3,17-dihydroxy-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,17-dodecahydrocyclopenta[a]phenanthren-16-one
• CAS: 1159-66-6
• 化学式: C₁₉H₂₈O₃
• 分子量: 304.43
• InChiKey: AKRBLZKRYPEVIK-PEMPUTJUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,8R,9S,10R,13S,14S,17R)-3,17-二羟基-10,13-二甲基-1,2,3,4,7,8,9,11,12,14,15,17-十二氢环戊烯并[a]菲-16-酮 生成 3β-hydroxy-5-androsten-16-one
  参考文献：
  名称：

  The germplasm release of F87084, a fertile, adapted clone with multiple disease resistances

  摘要：

  F87084 is a germplasm release that has been developed by conventional breeding methods and can be traced back to very diverse germplasm sources. This clone has excellent female fertility, round-oval tubers and is well adapted to Eastern Canada. The vine maturity is slightly later than that of Kennebec, and the mean marketable yield is 78% of Kennebec. The specific gravity, boil, bake and chip scores are somewhat lower than Kennebec. F87084 is resistant to late blight, Verticillium dahliae, early blight, and the pathotypes of wart occurring in Newfoundland. F87084 has extreme resistance to PVY degrees and PVX. It is also resistant to the potato cyst nematode pathotype Ro1. Progeny analyses indicate that F87084 is duplex for the genes controlling extreme resistance to PVX as well as resistance to the potato cyst nematode (Ro1).

  DOI：

  10.1007/bf02874769
• 作为产物：
  描述：

  androsta-5,16-diene-3β,17-diyl diacetate 在 lead(IV) acetate 、 氢氧化钾 作用下， 以 甲醇 、 溶剂黄146 为溶剂， 生成 (3S,8R,9S,10R,13S,14S,17R)-3,17-二羟基-10,13-二甲基-1,2,3,4,7,8,9,11,12,14,15,17-十二氢环戊烯并[a]菲-16-酮
  参考文献：
  名称：

  16氧化ANDROST-5-EN-3-BETA-OL衍生物的合成。

  摘要：

  约有16种含氧的雄甾-5-烯类固醇，它们均为类固醇代谢物，是通过3β-乙酰氧基-5α, 6β-二氯雄甾烷-17-酮制备的。

  DOI：

  10.1248/cpb.12.808

文献信息

• Production of 16β-(acetoxy)acetoxy derivatives by reaction of 17-keto steroid enol acetates with lead (IV) acetate
  作者：M Numazawa

  DOI：10.1016/s0039-128x(01)00103-9

  日期：2001.10

  16beta-acetoxy-17-ketones with the lead reagent did not yield the corresponding (acetoxy)acetates. Reaction of the enol acetate 3 with Pb(OCOCD(3))(4) in CD(3)COOD yielded principally the labeled (acetoxy)acetate 10-d(3), which had a CD(3)COOCH(2)COO moiety at C-16beta. In contrast, when the deuterated enol acetate 3-d(3), which was obtained by treatment of the 17-ketone 14 with (CD(3)CO)(2)O in the presence

  用 Pb(OCOCH(3))(4) 处理 3beta-acetoxyandrost-5-en-17-one 及其 5alpha-reduced 类似物 5alpha-androstan-17-one 和醋酸雌酮，1-4 的烯醇乙酸酯在乙酸和乙酸酐中得到先前未报道的产物 16β-（乙酰氧基）乙酰氧基-17-酮 8-10 和 12，产率 9-15%，以及已知的主要产物 16β-乙酰氧基-17-酮 5- 7 和 11。用先导试剂对 16β-乙酰氧基-17-酮进行类似处理没有产生相应的（乙酰氧基）乙酸盐。烯醇乙酸酯 3 与 Pb(OCOCD(3))(4) 在 CD(3)COOD 中的反应主要产生标记的（乙酰氧基）乙酸酯 10-d(3)，其具有 CD(3)COOCH(2)COO C-16beta 的部分。相反，当氘代烯醇乙酸酯 3-d(3) 时，通过在 LDA 存在下用 (CD(3)CO)(2)O 处理
• Carbon-13 nuclear magnetic resonance spectral data of steroidal vicinal ketols and related compounds
  作者：Darío Doller、Eduardo G. Gros

  DOI：10.1016/0039-128x(91)90077-9

  日期：1991.4

  Carbon-13 nuclear magnetic resonance spectra for 31 3 beta-hydroxy and acetoxy androstane derivatives bearing vicinal oxygenated functions at ring D with and without oxygenated functions at C-6 are reported. Relative substituent effects are discussed.

  报道了在环D处具有邻位氧化功能的31 3β-羟基和乙酰氧基雄烷衍生物的碳-13核磁共振光谱，在C-6处具有和不具有氧化功能。讨论了相对的取代基效应。
• Highly stereoselective synthesis of spiro-α-methylene-γ-butyrolactones: the role of α-hydroxy substitution
  作者：Mangesh S. Sawant、Rita Katoch、Girish K. Trivedi、Umesh R. Desai

  DOI：10.1039/a708558c

  日期：——

  An α-alkoxy substituent provides acceleration and greater diastereoselectivity in organometallic additions to chiral ketones. We find that α-hydroxy substitution also plays a similar role. Whereas the addition of a Reformatsky reagent to unsubstituted steroidal ketones does not yield the desired products, α-hydroxy substitution provides the α-methylene-γ-butyrolactone steroid in good yields and very high diastereoselectivity. The α-methylene-γ-butyrolactone moiety has been synthesized at several positions on the steroid nucleus. The stereochemistry can be explained through a chelated transition state, while the enhancement in the rate may be due to both the electron-withdrawing nature of the Reformatsky reagent and the neighbouring group effect.

  在手性酮的有机金属加成中，δ-烷氧基取代基具有加速和更高的非对映选择性。我们发现δ-羟基取代也起着类似的作用。将 Reformatsky 试剂加到未取代的甾酮中并不能得到所需的产物，而 δ-羟基取代则能以良好的产率和极高的非对映选择性得到 δ-亚甲基-δ-丁内酯甾酮。δ-亚甲基-δ-丁内酯分子是在类固醇核的多个位置上合成的。立体化学可通过螯合过渡态来解释，而速率的提高则可能是由于 Reformatsky 试剂的吸电子特性和邻近基团效应。
• Controlled alkaline hydrolysis of steroidal α-bromoketones: New conditions and synthesis of 2α-hydroxy-3-ones
  作者：Mitsuteru Numazawa、Masao Nagaoka

  DOI：10.1016/0039-128x(82)90152-0

  日期：1982.3

  Controlled alkaline hydrolysis of 16 alpha-bromo-17-keto steroids 1, 5 and 7 with potassium carbonate and tetra-n-butylammonium hydroxide (n-Bu4NOH) and synthesis of 2 alpha-hydroxy-3-ones 11, 13 and 16 by the controlled hydrolysis of the corresponding 2 alpha-bromo-3-ones 9, 12 and 15 are described. Treatment of the bromoketones 1,5 and 7 with potassium carbonate in aqueous acetone or with n-Bu4NOH

  用碳酸钾和四正丁基氢氧化铵（n-Bu4NOH）控制16种α-溴17-酮类固醇1、5和7的碱水解，并通过以下方法合成2α-羟基-3-酮11、13和16描述了相应的2个α-溴-3-酮9、12和15的受控水解。在丙酮水溶液中用碳酸钾或在二甲基甲酰胺水溶液（DMF）中用n-Bu4NOH处理溴酮1,5和7，分别以85-90％的产率得到16个α-羟基-17-酮3m 6和8。通过分别使用上述条件或氢氧化钠在吡啶或DMF中的高产率水解相应的溴代酮9、12和15，得到2个α-羟基-3-酮11、13和16。
• Mechanistic aspects of rearrangement of 16α-hydroxy-17-keto steroids to the 17β-hydroxy-16-keto isomers
  作者：Mitsuteru Numazawa、Masao Nagaoka、Hisao Matsuzaki、Kouwa Yamashita、Sachiko Komatsu、Yoshio Osawa

  DOI：10.1016/j.steroids.2008.03.001

  日期：2008.9

  the C-15 position (k(16,15)). The marked deuterium-isotope effect on each enolization was observed with k(H)/k(D) ranging between 5.4 and 8.8. The present findings reveal that the initial hydration-dehydration equilibration at the C-17 carbonyl of ketol 1 followed by enolization of the carbonyl gives the ene-diol intermediate that isomerizes quantitatively to the 16-keto isomer of which the 16-carbonyl

  碱催化重排 16alpha-羟基-17-酮类固醇 1 到 17beta-羟基-16-酮类固醇 2 的机制方面通过使用 (18) O-和氘标记实验阐明。(18)O-标记实验驳斥了先前提出的重排的宝石水合准双轴脱水机制，并支持传统的烯醇化机制。此外，在 C-17 羰基上比在 C-16 羰基上更有效地通过宝石-水合-脱水达到平衡。17β-酮醇 2 的 C-16 上的羰基朝向 C-17 位置 (k(16,17)) 的烯醇化率比朝向 C-16 位置的 16α-酮醇 1 高约 8-10 倍（ k(17,16)) 和酮醇 2 朝向 C-15 位置 (k(16,15))。在 k(H)/k(D) 范围在 5 之间时，观察到对每次烯醇化的显着氘同位素效应。4 和 8.8。目前的研究结果表明，酮醇 1 的 C-17 羰基处的初始水合-脱水平衡，随后羰基的烯醇化产生了烯二醇中间体，该中间体定量异构化为 16-酮异构体，其中