all syn-trans-1,15-quinquecyclopropanedimethanol | 181182-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: all syn-trans-1,15-quinquecyclopropanedimethanol
• 英文别名: [(1R,2S)-2-[(1R,2R)-2-[(1R,2R)-2-[(1R,2R)-2-[(1S,2R)-2-(hydroxymethyl)cyclopropyl]cyclopropyl]cyclopropyl]cyclopropyl]cyclopropyl]methanol
• CAS: 181182-35-4
• 化学式: C₁₇H₂₆O₂
• 分子量: 262.392
• InChiKey: QOCMGHHRCWSYEB-VQRDVQGMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  all syn-trans-1,15-quinquecyclopropanedimethanol 在 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (E)-3-[(1R,2S,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''R,2''''S)-2''''-((E)-3-Hydroxy-propenyl)-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2-yl]-prop-2-en-1-ol
  参考文献：
  名称：

  迭代环丙烷化：六环丙烷胆固醇酯转移蛋白抑制剂 U-106305 全合成的简洁策略

  摘要：

  第一个对映选择性全合成六环丙烷天然产物 U-106305，由 Streptomyces sp. 产生。UC 11136 进行了详细描述。考虑到 U-106305 的生物合成及其与五环丙烷细菌代谢物 FR-900848 (10) 的相似性，建议其先前未知的立体结构应表示为 11。11 的中央 C2 对称五环丙烷单元由以有效的双向方法重复使用三步环丙烷“同源”序列。去对称的五环丙烷 23 被转化为二烯醇 13，二烯醇 13 被立体和区域选择性地单环丙烷化以提供六环丙烷 25。通过转化为硫醚 29 和脱硫来实现脱氧。

  DOI：

  10.1021/ja9708326
• 作为产物：
  描述：

  bis(iodomethyl)zinc 、 (E)-3-[(1S,2R)-2-[(1R,2R)-2-[(1R,2S)-2-[(E)-3-hydroxyprop-1-enyl]cyclopropyl]cyclopropyl]cyclopropyl]prop-2-en-1-ol 在 2-丁基-1,3,2-二氧硼戊环-4S,5S-二羧酸双(二甲氨基化合物) 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 17.0h， 生成 all syn-trans-1,15-quinquecyclopropanedimethanol
  参考文献：
  名称：

  迭代环丙烷化：六环丙烷胆固醇酯转移蛋白抑制剂 U-106305 全合成的简洁策略

  摘要：

  第一个对映选择性全合成六环丙烷天然产物 U-106305，由 Streptomyces sp. 产生。UC 11136 进行了详细描述。考虑到 U-106305 的生物合成及其与五环丙烷细菌代谢物 FR-900848 (10) 的相似性，建议其先前未知的立体结构应表示为 11。11 的中央 C2 对称五环丙烷单元由以有效的双向方法重复使用三步环丙烷“同源”序列。去对称的五环丙烷 23 被转化为二烯醇 13，二烯醇 13 被立体和区域选择性地单环丙烷化以提供六环丙烷 25。通过转化为硫醚 29 和脱硫来实现脱氧。

  DOI：

  10.1021/ja9708326

文献信息

• Total Synthesis and Stereochemical Assignment of the Quinquecyclopropane-Containing Cholesteryl Ester Transfer Protein Inhibitor U-106305
  作者：Anthony G. M. Barrett、Dieter Hamprecht、Andrew J. P. White、David J. Williams

  DOI：10.1021/ja961399n

  日期：1996.1.1
• Two-Directional Synthesis of Polycyclopropanes. An Approach to the Quinquecyclopropane Fragment of U-106305
  作者：W. Scott McDonald、Christopher A. Verbicky、Charles K. Zercher

  DOI：10.1021/jo961136b

  日期：1997.3.1

  The stereoselective preparation of three stereoisomeric tercyclopropanes and a quinquecyclopropane was investigated. Two of the tercyclopropanes were C-2-symmetric and were prepared efficiently through the two-directional application of Charette's reagent-stereocontrolled cyclopropanation methodology. The nonsymmetric tercyclopropane was prepared by an iterative one-directional application of the same reagent-mediated cyclopropanation method. It was shown that the reagent-controlled transformations are far more effective for the stereoselective preparation of the tercyclopropanes than are the reactions which rely upon the influence of the substrate stereocenters. A C-2-symmetric quinquecyclopropane, which possesses the repeating trans-syn stereochemistry, was prepared by iterative application of the two-directional strategy.
• Synthesis and Characterization of Coronanes:  Multicyclopropane-Fused Macrocyclic Arrays
  作者：Anthony G. M. Barrett、Dieter Hamprecht、Rachel A. James、Mitsuru Ohkubo、Panayiotis A. Procopiou、Miguel A. Toledo、Andrew J. P. White、David J. Williams

  DOI：10.1021/jo001167d

  日期：2001.4.1

  Stepwise macrocyclization of the all syn-trans-1,15-quinquecyclopropanedimethanol (4) with iso- and terephthaloyl chlorides and 4,4'-methanediyl-dibenzoic acid (28) gave the corresponding coronanes 22, 23, and 32. The same protocol was used with all syn-trans-1,21-septecyclopropanedimethanol (5) and 2,3-naphthalenedicarboxylic acid to obtain the macrolide 27. Direct macrocyclization of diol 4 and 1,10-phenanthroline-2,9-dicarbonyl chloride (33) and 2,2'-bipyridine-4,4'-dicarbonyl chloride (35) gave the coronanes 34 and 36, respectively. Ring closing metathesis (RCM) of the diene 42 using Cl-2(Cy3P)(2)Ru=CHPh (48) (Grubbs's catalyst) gave the macrocyclic lactone 45. The structures of coronanes 22, 23, 32, 34, 36, and 45 were confirmed by X-ray crystallographic studies which showed the cyclopropyl chain to adopt very differing conformations throughout the series. Several of the macrocycles have significant free pathways through their ring centers, and in the case of compound 34 there is a water molecule hydrogen bonded within the ring. This latter compound has the potential to act as a chiral ligand to metal centers.