4β-formyl-17β-acetoxy-5β-androstane

• 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: 4β-formyl-17β-acetoxy-5β-androstane
• 英文别名: [(4S,5R,8R,9S,10R,13S,14S,17S)-4-formyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-17-yl] acetate
• 化学式: C₂₂H₃₄O₃
• 分子量: 346.51
• InChiKey: NVRGGGSKGNUZHX-KCTWHOTLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  睾酮 在 2-叔丁基苯酚亚磷酸盐 、 铑 吡啶 、 sodium tetrahydroborate 、 Montmorillonite 、 氢气 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 100.0 ℃ 、2.0 MPa 条件下， 反应 56.0h， 生成 4β-formyl-17β-acetoxy-5β-androstane
  参考文献：
  名称：

  Diastereoselective hydroformylation of Δ4-steroids with rhodium–phosphite catalysts

  摘要：

  The hydroformylation of two steroidal substrates, namely 17 beta -acetoxyandrost-4-ene 1 and 3 beta, 17 beta -diacetoxyandrost-4-ene 2, with a rhodium tris(O-tert-butylphenyl)phosphite catalyst was investigated. In both cases, the major reaction product was 4 beta -formyl-17 beta -acetoxy-5 beta -androstane 3, which was isolated and characterized by X-ray diffraction and NMR techniques. This reaction is the first example of catalytic carbonylation to the beta face of a steroid backbone. The effect of reaction temperature, the pressure at which the reaction was completed and the ligand:Rh ratio on the regio- and stereoselectivity of the reaction is also discussed. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00191-4

文献信息

• Highly efficient Rh(I)/tris-binaphthyl monophosphite catalysts for hydroformylation of sterically hindered alkyl olefins
  作者：Gonçalo N. Costa、Rui M.B. Carrilho、Lucas D. Dias、Júlio C. Viana、Gilberto L.B. Aquino、Marta Pineiro、Mariette M. Pereira

  DOI：10.1016/j.molcata.2016.02.016

  日期：2016.5

  Abstract The hydroformylation of highly substituted alkyl olefins was efficiently performed, with use of rhodium(I)/tris-binaphthyl monophosphite catalysts, containing different ether substituents at the 2′-binaphthyl position (OMe, OBn, OCHPh 2 and OAdamantyl). A systematic kinetic study, carried out for hydroformylation of methyl non-3-enoate, has shown a significant influence of the ligand’s OR group

  摘要 使用在 2'-联萘位置（OMe、OBn、OCHPh 2 和 OAdamantyl）含有不同醚取代基的铑 (I)/三联萘单亚磷酸酯催化剂有效地进行了高度取代的烷基烯烃的加氢甲酰化。对非 3-烯酸甲酯的加氢甲酰化进行的系统动力学研究表明，配体的 OR 基团对铑催化剂的性能有显着影响，Rh(I)/tris[2'-benzyloxy-1, 1'-联萘-2-基]亚磷酸酯催化体系 (Rh(I)/ L2 -OBn) 对醛类化合物具有最高的化学选择性，对 C-5 甲酰基产物具有最高的区域选择性。该催化体系进一步应用于天然产物的负载CC双键的加氢甲酰化，即油酸甲酯、(-)-异胡薄荷醇苄基醚和17β-acetoxyandrost-4-ene，
• Diastereoselective hydroformylation of Δ4-steroids with rhodium–phosphite catalysts
  作者：Zoraida Freixa、Mariette M Pereira、J.Carles Bayón、Artur M.S Silva、Jorge A.R Salvador、Ana Matos Beja、José A Paixão、Manuela Ramos

  DOI：10.1016/s0957-4166(01)00191-4

  日期：2001.5

  The hydroformylation of two steroidal substrates, namely 17 beta -acetoxyandrost-4-ene 1 and 3 beta, 17 beta -diacetoxyandrost-4-ene 2, with a rhodium tris(O-tert-butylphenyl)phosphite catalyst was investigated. In both cases, the major reaction product was 4 beta -formyl-17 beta -acetoxy-5 beta -androstane 3, which was isolated and characterized by X-ray diffraction and NMR techniques. This reaction is the first example of catalytic carbonylation to the beta face of a steroid backbone. The effect of reaction temperature, the pressure at which the reaction was completed and the ligand:Rh ratio on the regio- and stereoselectivity of the reaction is also discussed. (C) 2001 Elsevier Science Ltd. All rights reserved.