(8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrospiro[cyclopenta[a]phenanthrene-17,2'-oxetane] | 16377-13-2

• 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: (8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrospiro[cyclopenta[a]phenanthrene-17,2'-oxetane]
• 英文别名: (8R,9S,13S,14S,17R)-3-methoxy-13-methylspiro[7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthrene-17,2'-oxetane]
• CAS: 16377-13-2
• 化学式: C₂₁H₂₈O₂
• 分子量: 312.452
• InChiKey: UFDFNEJCICPHFU-CRSSMBPESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrospiro[cyclopenta[a]phenanthrene-17,2'-oxetane] 在 三甲基氯硅烷 、 Ti(OⁱPr)[{(O-2,4-Me₂C₆H₂)-6-CH₂}₃N] 、 1,4-环己二烯 、 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以96%的产率得到2-[(8S,9S,13R,14S,17R)-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-yl]ethanol
  参考文献：
  名称：

  Titanatrane生成的低价钛物种及其催化反应：氧杂环丁烷的自由基开环

  摘要：

  AbstractTreatment of a titanatrane complex with trimethylsilyl chloride and magnesium powder in tetrahydrofuran generated a low‐valent titanium species. This species catalyzed the radical ring opening of epoxides and oxetanes to produce the corresponding less substituted alcohols. The reagent also catalyzed the deallylation and depropargylation of allylic and propargylic ethers, respectively, to provide the parent alcohols.magnified image

  DOI：

  10.1002/adsc.201300368
• 作为产物：
  描述：

  3-甲氧基雌酮 、 S-methyl-S-(sodiomethyl)-N-(4-tolylsulfonyl)sulfoximide 以 二甲基亚砜 为溶剂， 反应 20.0h， 生成 (8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrospiro[cyclopenta[a]phenanthrene-17,2'-oxetane] 、 (8R,9S,13S,14S)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydrospiro[cyclopenta[a]phenanthrene-17,2'-oxetane]
  参考文献：
  名称：

  Synthesis of 2,2-disubstituted oxetanes from ketones with S-methyl-S-(sodiomethyl)-N-(4-tolylsulfonyl)sulfoximine

  摘要：

  DOI：

  10.1021/ja00340a019

文献信息

• Catalytic Regioselective Isomerization of 2,2‐Disubstituted Oxetanes to Homoallylic Alcohols
  作者：Albert Cabré、Sergi Rafael、Giuseppe Sciortino、Gregori Ujaque、Xavier Verdaguer、Agustí Lledós、Antoni Riera

  DOI：10.1002/anie.201915772

  日期：2020.5.4

  mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C6 F5 )3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ-chiral

  应变杂环化合物的选择性异构化是有机合成中的重要工具。描述了前所未有的2，2-二取代的氧杂环丁烷向选择性烯丙基的区域选择性异构化。使用三（五氟苯基）硼烷（B（C6 F5）3），市售的路易斯酸是获得良好收率和选择性的关键，因为其他路易斯酸提供了异构体和大量聚合的混合物。该反应在异常温和的反应条件下和非常低的催化剂负载量（0.5mol％）下进行。DFT计算揭示了异构化的机理特征，并说明了由B（C6 F5）3催化剂显示出的高选择性。
• Synthesis of 2,2-disubstituted oxetanes from ketones with S-methyl-S-(sodiomethyl)-N-(4-tolylsulfonyl)sulfoximine
  作者：Steven C. Welch、A. S. C. Prakasa Rao、John T. Lyon、Jean Marie Assercq

  DOI：10.1021/ja00340a019

  日期：1983.1
• Generation of a Low-Valent Titanium Species from Titanatrane and its Catalytic Reactions: Radical Ring Opening of Oxetanes
  作者：Naoto Takekoshi、Kenji Miyashita、Noriaki Shoji、Sentaro Okamoto

  DOI：10.1002/adsc.201300368

  日期：2013.8.12

  AbstractTreatment of a titanatrane complex with trimethylsilyl chloride and magnesium powder in tetrahydrofuran generated a low‐valent titanium species. This species catalyzed the radical ring opening of epoxides and oxetanes to produce the corresponding less substituted alcohols. The reagent also catalyzed the deallylation and depropargylation of allylic and propargylic ethers, respectively, to provide the parent alcohols.magnified image