(25R)-3-oxa-6β-acetoxy-5-hydroxy-4a-homo-5α-spirostan-4-one | 909879-53-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (25R)-3-oxa-6β-acetoxy-5-hydroxy-4a-homo-5α-spirostan-4-one
• 英文别名: (25R)-A-homo-2a-oxa-6β-acetoxy-5-hydroxy-5α-spirostan-3-one；[(1S,2S,4S,5'R,6R,7S,8R,9S,12S,13R,19R,20R)-19-hydroxy-5',7,9,13-tetramethyl-17-oxospiro[5,16-dioxapentacyclo[10.9.0.02,9.04,8.013,19]henicosane-6,2'-oxane]-20-yl] acetate
• CAS: 909879-53-4
• 化学式: C₂₉H₄₄O₇
• 分子量: 504.664
• InChiKey: NRNIJYASKQOFIO-UGUMFSMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  36
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (25R)-3-oxa-6β-acetoxy-5-hydroxy-4a-homo-5α-spirostan-4-one 在 lithium hydroxide 、 硫酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 生成 (25R)-2,3-seco-6β-acetoxy-2(5)-oxa-5α-spirostan-3-oic acid
  参考文献：
  名称：

  Synthesis of peptidomimetic-spirostane hybrids via Ugi reaction: a versatile approach for the formation of peptide–steroid conjugates

  摘要：

  A general approach towards the preparation of peptide-steroid conjugates has been addressed. Utilizing the Ugi reaction, five peptidomimetic-steroid hybrids were achieved in good to excellent yields from carboxy- and amino-spirostanes and mono-protected alpha-amino acids. Diverse synthetic routes, specially focused on the formation of secosteroids, were implemented to introduce Ugi-type functionalities at different positions of the steroidal nucleus. This versatile approach is suitable for the formation of stable conjugates of steroids with other biologically relevant molecules. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.050
• 作为产物：
  描述：

  (2R,2aR,4S,5'R,6aR,6bS,8aS,8bR,9S,10R,11aS,12aS,12bS)-4-((tert-butyldimethylsilyl)oxy)-2a-hydroxy-5',6a,8a,9-tetramethyldocosahydrospiro[naphtho[2',1':4,5]indeno[2,1-b]furan-10,2'-pyran]-2-yl acetate 在 四丁基氟化铵 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (25R)-3-oxa-6β-acetoxy-5-hydroxy-4a-homo-5α-spirostan-4-one
  参考文献：
  名称：

  Synthesis of peptidomimetic-spirostane hybrids via Ugi reaction: a versatile approach for the formation of peptide–steroid conjugates

  摘要：

  A general approach towards the preparation of peptide-steroid conjugates has been addressed. Utilizing the Ugi reaction, five peptidomimetic-steroid hybrids were achieved in good to excellent yields from carboxy- and amino-spirostanes and mono-protected alpha-amino acids. Diverse synthetic routes, specially focused on the formation of secosteroids, were implemented to introduce Ugi-type functionalities at different positions of the steroidal nucleus. This versatile approach is suitable for the formation of stable conjugates of steroids with other biologically relevant molecules. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.06.050

文献信息

• Studies on the regioselectivity of the Baeyer-Villiger reaction of 3-keto steroids: Conformational effects determine the migration aptitude
  作者：Daniel G. Rivera、Orlando Pando、Reynier Suardiaz、Francisco Coll

  DOI：10.1016/j.steroids.2007.01.002

  日期：2007.5

  completely unselective for 3-keto-5beta-steroids by using m-chloroperoxybenzoic acid. Theoretical studies were performed to explain the regiochemistry of this process, which is suggested to be controlled by conformational effects in the transition state of the Criegee rearrangement.

  通过使用间氯过氧苯甲酸和三氟过氧乙酸作为氧化剂，对 3-酮类固醇的 Baeyer-Villiger 反应进行了详细研究。该过程在使用两种过酸的情况下对 3-keto-5alpha-类固醇具有完全区域特异性，并且通过使用三氟过氧乙酸仅对 3-keto-5beta-类固醇具有部分区域选择性。有趣的是，通过使用间氯过氧苯甲酸，该反应对 3-keto-5beta-类固醇完全没有选择性。进行了理论研究以解释该过程的区域化学，这表明该过程受 Criegee 重排过渡态中的构象效应控制。