[(1S,2R,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''S,2''''R)-2-(tert-Butyl-dimethyl-silanyloxymethyl)-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2''''-yl]-methanol | 181182-36-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: [(1S,2R,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''S,2''''R)-2-(tert-Butyl-dimethyl-silanyloxymethyl)-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2''''-yl]-methanol
• CAS: 181182-36-5
• 化学式: C₂₃H₄₀O₂Si
• 分子量: 376.655
• InChiKey: TUNAJHIBUNCSQI-XTKPIWSKSA-N

物化性质

• 沸点：
  426.3±18.0 °C(predicted)
• 密度：
  1.102±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.18
• 重原子数：
  26.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [(1S,2R,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''S,2''''R)-2-(tert-Butyl-dimethyl-silanyloxymethyl)-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2''''-yl]-methanol 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 N,N'-二环己基碳二亚胺 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 Isophthalic acid mono-((1S,2R,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''S,2''''R)-2''''-hydroxymethyl-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2-ylmethyl) ester
  参考文献：
  名称：

  Synthesis and Characterization of Coronanes:  Multicyclopropane-Fused Macrocyclic Arrays

  摘要：

  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.

  DOI：

  10.1021/jo001167d
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 all syn-trans-1,15-quinquecyclopropanedimethanol 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 以58%的产率得到[(1S,2R,1'R,2'R,1''R,2''R,1'''R,2'''R,1''''S,2''''R)-2-(tert-Butyl-dimethyl-silanyloxymethyl)-[1,2';1',1'';2'',1''';2''',1'''']quinquecyclopropan-2''''-yl]-methanol
  参考文献：
  名称：

  Synthesis and Characterization of Coronanes:  Multicyclopropane-Fused Macrocyclic Arrays

  摘要：

  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.

  DOI：

  10.1021/jo001167d

文献信息

• Iterative Cyclopropanation:  A Concise Strategy for the Total Synthesis of the Hexacyclopropane 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/ja9708326

  日期：1997.9.1

  The first enantioselective total synthesis of the hexacyclopropane natural product U-106305, which is produced by Streptomyces sp. UC 11136, is described in full detail. Considerations on the biosynthesis of U-106305 and its close resemblance to the pentacyclopropane bacterial metabolite FR-900848 (10) led to the proposal that its previously unknown stereostructure should be represented as 11. The

  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。
• 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
• Multiple Asymmetric Cyclopropanation: Synthesis and X-Ray Crystallographic Studies of a Prototype Coronane and all anti-trans-1,15-Quinquecyclopropanedimethanol
  作者：Anthony G. M. Barrett

  DOI：10.1055/s-1998-5930

  日期：1998.3