cholest-5-en-3α-ol benzoate | 42921-42-6

• 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
• 英文名称: cholest-5-en-3α-ol benzoate
• 英文别名: 3α-cholersteryl benzoate；3α-cholesteryl benzoate；3-Epicholesteryl benzoate；Epicholesterol benzoate；benzoic acid-(cholesten-(5)-yl-(3α)-ester)；Benzoesaeure-(cholesten-(5)-yl-(3α)-ester)；[(3R,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl] benzoate
• CAS: 42921-42-6
• 化学式: C₃₄H₅₀O₂
• 分子量: 490.77
• InChiKey: UVZUFUGNHDDLRQ-VUARJUAMSA-N

物化性质

• 熔点：
  163.5-165.0 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  563.6±29.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cholest-5-en-3α-ol benzoate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 以48%的产率得到表胆甾醇
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.

  DOI：

  10.1021/jo00085a037
• 作为产物：
  描述：

  cholesterol 在 吡啶 、 aluminum isopropoxide 、 苯 作用下， 生成 cholest-5-en-3α-ol benzoate
  参考文献：
  名称：

  Barnett et al., Journal of the Chemical Society, 1940, p. 1390,1392

  摘要：

  DOI：

文献信息

• A Highly β-Stereoselective Catalytic Epoxidation of Δ⁵-Unsaturated Steroids with a Novel Ruthenium(II) Complex under Aerobic Conditions
  作者：Venkitasamy Kesavan、Srinivasan Chandrasekaran

  DOI：10.1021/jo980829k

  日期：1998.10.1

  6alpha-epoxides as the major products. The overall conformation of the steroid nucleus is nearly planar in the cholesteryl ester, while it is bent at the junction between the rings A and B in the 5beta,6beta-epoxide. This change from pseudo-trans- to cis-stereochemistry of the A-B ring junction provides more room for the catalyst to approach from the beta-face of the steroidal skeleton.

  Delta（5）-不饱和类固醇衍生物的催化β-立体选择性环氧化已在有氧条件下通过新型钌（II）生物恶唑啉配合物实现。反应是区域选择性和立体选择性的。反应条件以非常好的收率提供了具有高度立体选择性（88-96％）的相应的5β，6β-环氧化物，而甾醇衍生物与过酸的氧化导致5α，6α-环氧化物作为主要产物。类固醇核的整体构象在胆固醇酯中几乎是平面的，而在5beta，6beta-环氧化物的环A和B之间的连接处弯曲。从AB环连接的伪反式到顺式立体化学的这种变化为催化剂从甾体骨架的β面接近提供了更多空间。
• Allylic and Homoallylic CD Exciton Chirality: A Sensitive Method for Determining the Absolute Stereochemistry of Natural Products
  作者：Hans-Ulrich Humpf、Nina Berova、Koji Nakanishi、Michael B. Jarstfer、C. Dale Poulter

  DOI：10.1021/jo00116a048

  日期：1995.6
• Inversion of secondary chiral alcohols in toluene with the tunable complex of R3NR′COOH
  作者：Xiao-Xin Shi、Chun-Li Shen、Jian-Zhong Yao、Liang-Deng Nie、Na Quan

  DOI：10.1016/j.tetasy.2009.12.028

  日期：2010.3

  The S(N)2 reaction of enantiomerically pure sulfonates with the tunable complex of R3N-R'COOH in toluene has been extensively studied. It was revealed that the molar ratio of the tertiary amines and carboxylic acids in the complex of R3NR'COOH is crucial for the S(N)2 reaction, and should be tuned for each sulfonate to give the best yield. Fifteen sulfonates 1 and 3-13 (Scheme 2) were prepared and transformed into 22 corresponding inverted esters 2 and 14-24 (Scheme 2) in good to high yields. (C) 2010 Elsevier Ltd. All rights reserved.
• A novel and highly .beta.-selective epoxidation of .DELTA.5-unsaturated steroids with permanganate ion
  作者：M. S. Syamala、Jagattaran Das、Sundarababu Baskaran、Srinivasan Chandrasekaran

  DOI：10.1021/jo00032a059

  日期：1992.3
• Desorption chemical ionization mass spectrometry of epimeric 3-hydroxysteroids and derivatives. Stereoselectivity and nucleophilic substitution with ammonia
  作者：Pierre Tecon、Yutaka Hirano、Carl Djerassi

  DOI：10.1002/oms.1210170608

  日期：1982.6

  AbstractThe desorption chemical ionization mass spectra, using ammonia as reagent gas, of several epimeric 3‐hydroxysteroids and their ether and carboxylic acid ester derivatives are reported. In the case of steroids possessing a Δ4‐ or Δ5‐3α‐benzoate moiety, stereospecific stabilization of the protonated molecular ion [M+H]+ is observed. This behavior is rationalized in terms of interaction of the double bond and the protonated benzoate group at C‐3. Nucleophilic substitution by NH3 is observed when a double bond is present in the vicinity of the substitution center. The nature and the stereochemistry of the leaving group influence this substitution reaction. Our results seem to indicate the operation of a two‐step mechanism (e.g. SN1 type reaction) rather than a SN2 type mechanism for the formation of the substitution ion [MOR+NH3]+.