3,3-ethanediyldioxy-5,6β-epoxy-5β-cholestane | 6215-57-2

• 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
• 英文名称: 3,3-ethanediyldioxy-5,6β-epoxy-5β-cholestane
• 英文别名: 3,3-Aethandiyldioxy-5,6β-epoxy-5β-cholestan；5β,6β-epoxycholestane-3-one 3-ethylene ketal；(1'S,2'R,7'S,9'R,11'S,12'S,15'R,16'R)-2',16'-dimethyl-15'-[(2R)-6-methylheptan-2-yl]spiro[1,3-dioxolane-2,5'-8-oxapentacyclo[9.7.0.02,7.07,9.012,16]octadecane]
• CAS: 6215-57-2
• 化学式: C₂₉H₄₈O₃
• 分子量: 444.698
• InChiKey: KGPVETFFXMOEJP-KWAJGNIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  31
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,3-ethanediyldioxy-5,6β-epoxy-5β-cholestane 在 aluminum isopropoxide 作用下， 以 甲苯 为溶剂， 反应 72.0h， 以0.056 g的产率得到4-胆甾烯-6-醇-3-酮
  参考文献：
  名称：

  Holland, Herbert L.; Khan, Saeed R., Canadian Journal of Chemistry, 1985, vol. 63, p. 2763 - 2768

  摘要：

  DOI：
• 作为产物：
  描述：

  (8S,9S,10R,13R,14S,17R)-10,13-二甲基-17-[(2R)-6-甲基庚烷-2-基]螺[1,2,4,7,8,9,11,12,14,15,16,17-十二氢环戊烯并[a]菲-3,2'-1,3-二氧戊环] 在 dichlororuthenium(IV) meso-tetrakis(2,6-dichlorophenyl)porphyrin 2,6-二氯吡啶N-氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以94%的产率得到3,3-ethanediyldioxy-5,6β-epoxy-5β-cholestane
  参考文献：
  名称：

  介孔四（2,6-二氯苯基）卟啉的二氯钌（IV）络合物：活性强的催化剂，可通过使用2,6-二氯吡啶N-氧化物高度选择性氧化芳烃，不饱和类固醇和缺电子的烯烃。

  摘要：

  由[Ru（VI）（2,6-Cl2tpp）O2]与Me3SiCl的反应以90％的收率制备的[Ru（IV）（2,6-Cl2tpp）Cl2]是通过X射线晶体学表征的结构明显优于[Ru（IV）（tmp）Cl2]，[Ru（IV）（ttp）Cl2]和[Ru（II）（por）（CO）]（por = 2,6-Cl2tpp，F20-tpp ，F28-tpp）作为烯烃与2,6-Cl2pyNO（2,6-Cl2tpp = meso-tetrakis（2,6-dichlorophenyl）porphyrinato dianion; tmp = meso-tetramesitylporphyrinato dianion; ttp = meso-tetrakis（对甲苯基）卟啉二价阴离子; F20-tpp =间四（五氟苯基）卟啉二价阴离子; F28-tpp = 2,3,7,8,12,13,17,18-八氟-5,10,15

  DOI：

  10.1002/chem.200401008

文献信息

• A Convenient Synthesis of 5,6β-Epoxides of Some Cholesteryl Esters and Δ⁵-Ketosteroid Derivatives by Catalytic β-Stereoselective Epoxidation
  作者：Jean-Claude Marchon、René Ramasseul

  DOI：10.1055/s-1989-27261

  日期：——

  The epoxidation of a series of cholesteryl esters by air in the presence of a catalytic amount of a ruthenium tetramesitylporphyrin complex is described. The preparative procedure, which requires only 4 to 5 mol % of the catalyst, leads to high conversion (76 to 94 %) and very high β-stereoselectivity (> 99 %). Similar results are obtained in the epoxidation of 3β-acetoxyandrost-5-ene-17-one, 3β-acetoxypregn-5-ene-20-one, and 3,3-ethylenedioxycholest-5-ene.

  报道了在四甲基卟啉钌络合物催化剂存在下，空气对一系列胆固醇酯进行环氧化反应的研究。该制备方法仅需加入4至5摩尔%的催化剂，即可实现高转化率（76至94%）和极高β立体选择性（> 99%）。类似的结果也在3β-乙酰氧基雄甾-5-烯-17-酮、3β-乙酰氧基孕甾-5-烯-20-酮和3,3-亚乙二氧基胆甾-5-烯的环氧化反应中获得。
• Reactions of epoxides—IX
  作者：J.W. Blunt、M.P. Hartshorn、D.N. Kirk

  DOI：10.1016/s0040-4020(01)99438-4

  日期：1966.1

  undergoes a novel ring A cleavage reaction with boron trifluoride. The 5α,6α-epoxide (IV) gives the expected A-homo-B-nor-4a-ketone, which undergoes further reactions involving the ketal group. The 6α-hydrogen-5β,6β-epoxide (XIIIa) rearranges to give mainly 5α-6-ketonic products, together with 6% of the A-seco-diene (XV). Mechanisms are suggested for these various reactions.

  3,3-乙二氧基-6α-甲基-5β，6β-环氧化物（I）与三氟化硼发生新的A环裂解反应。5α，6α-环氧化合物（IV）产生预期的A-homo-B-nor-4a-酮，该酮进一步经历涉及缩酮基的反应。6α-氢-5β，6β-环氧化物（XIIIa）重排，主要生成5α-6-酮化合物，以及6％的A-癸二烯（XV）。建议了各种反应的机理。
• Rearrangement of steroidal epoxides and opening of steroidal ketals by alkyllithiums
  作者：Herbert L. Holland、Jahangir

  DOI：10.1016/s0040-4039(00)81714-1

  日期：——

  The ethylene ketal of 5,6α-epoxycholestan-3-one is converted to a ketalised Δ4-6α-ol on treatment with n-BuLi. However, the corresponding β epoxide undergoes opening of the ketal ring in the same reaction. Methyl- and n-butyl-lithium also react with the ethylene ketal of 3-ketocholestanes to give 3-alkyl cholestan-3-ols. The stereoselectivity of this reaction is discussed and a mechanism involving

  5,6α-epoxycholestan -3-酮的亚乙基缩酮被转化为ketalisedΔ 4 -6α醇上治疗用n-BuLi。然而，在相同反应中，相应的β-环氧化物经历了缩酮环的打开。甲基和正丁基锂也与3-酮胆甾醇的乙烯缩酮反应，生成3-烷基胆甾烷-3-醇。讨论了该反应的立体选择性，并提出了涉及1,2氢化物位移的机理。
• Highly β‐Selective Epoxidation of Δ ⁵ ‐Unsaturated Steroids Catalyzed by Ketones
  作者：Dan Yang、Guan‐Sheng Jiao

  DOI：10.1002/1521-3765(20001002)6:19<3517::aid-chem3517>3.0.co;2-#

  日期：2000.10.2

  A general catalytic and environmentally friendly method for beta-epoxidation of Delta(5)-unsaturated steroids has been developed, which uses ketones as the catalysts and Oxone as the terminal oxidant. A whole range of Delta(5)-unsaturated steroids, which bear different functional groups such as hydroxyl, carbonyl, acetyl, or ketal, as well as different side chains, were conveniently converted to the corresponding synthetically and biologically interesting 5 beta,5 beta-epoxides with excellent beta-selectivities and high yields.
• Cooley et al., Journal of the Chemical Society, 1957, p. 4112,4114
  作者：Cooley et al.

  DOI：——

  日期：——