6,6-di-tert-butyl-hexahydro-1,3,5,7-tetraoxa-6-sila-benzo[g]cyclopropa[cd]inden-2-one | 361456-14-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: 6,6-di-tert-butyl-hexahydro-1,3,5,7-tetraoxa-6-sila-benzo[g]cyclopropa[cd]inden-2-one
• 英文别名: (1S,2R,5S,6R,7R,9R)-12,12-ditert-butyl-3,8,11,13-tetraoxa-12-silatetracyclo[7.4.0.02,6.05,7]tridecan-4-one
• CAS: 361456-14-6
• 化学式: C₁₆H₂₆O₅Si
• 分子量: 326.465
• InChiKey: PAUJUMUVQXIEHL-OJEZURLMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.38
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,6-di-tert-butyl-hexahydro-1,3,5,7-tetraoxa-6-sila-benzo[g]cyclopropa[cd]inden-2-one 在 吡啶 、 三氟化硼乙醚 、 铜 、 氟化氢吡啶 、 sodium iodide 、 锌 、 烯丙基三甲基硅烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 50.86h， 生成 4-hydroxy-6-vinyl-tetrahydro-furo[3,4-b]furan-2-one
  参考文献：
  名称：

  Intramolecular Cyclopropanation of Glycals:  Studies toward the Synthesis of Canadensolide, Sporothriolide, and Xylobovide

  摘要：

  [GRAPHICS]The first examples of copper-catalyzed intramolecular cyclopropanations of glycal-derived diazoacetates are reported. The new cyclopropanes are converted Into advanced intermediates for the synthesis of bislactone natural products. Synthetic highlights include the selective monodeprotection of a di-tert-butylsilylene ether and a zinc-mediated ring opening cascade reaction.

  DOI：

  10.1021/ol016239h
• 作为产物：
  描述：

  4,6-O-di(tert-butyl)silanediyl-D-glucal 在 bis(N-tert-butylsalicylaldiminato)copper(II) 、 N,N-二甲基苯胺 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 14.17h， 生成 6,6-di-tert-butyl-hexahydro-1,3,5,7-tetraoxa-6-sila-benzo[g]cyclopropa[cd]inden-2-one
  参考文献：
  名称：

  Intramolecular Cyclopropanation of Glycals:  Studies toward the Synthesis of Canadensolide, Sporothriolide, and Xylobovide

  摘要：

  [GRAPHICS]The first examples of copper-catalyzed intramolecular cyclopropanations of glycal-derived diazoacetates are reported. The new cyclopropanes are converted Into advanced intermediates for the synthesis of bislactone natural products. Synthetic highlights include the selective monodeprotection of a di-tert-butylsilylene ether and a zinc-mediated ring opening cascade reaction.

  DOI：

  10.1021/ol016239h

文献信息

• Acetal formation by solvolysis of glucal-derived donor–acceptor cyclopropanes
  作者：Ming Yu、Brian L. Pagenkopf

  DOI：10.1016/s0040-4020(03)00376-4

  日期：2003.4

  The conversion of glucal derived donor–acceptor cyclopropanes to acetals by TiCl4 mediated ring opening and alcohol trapping is described. Good selectivity for the alpha anomer and yields near 90% are consistently observed with aliphatic, benzylic and allylic alcohols, phenols and thiophenols. The utility of this method to prepare oligosaccharides through intermediate O,S-acetals is illustrated.

  描述了通过TiCl 4介导的开环和酒精捕集，将葡萄糖衍生的供体-受体环丙烷转化为缩醛。用脂肪族，苯甲醇和烯丙基醇，酚和硫酚始终可以观察到对α端基异构体的良好选择性，收率接近90％。说明了该方法通过中间体O，S-乙缩醛制备寡糖的实用性。
• Formal [3 + 2] Cycloadditions of Donor−Acceptor Cyclopropanes and Nitriles
  作者：Ming Yu、Brian L. Pagenkopf

  DOI：10.1021/ja029716f

  日期：2003.7.1

  Donor-acceptor cyclopropanes activated with Me3SiOTf cleave to reactive intermediates that can be efficiently intercepted by nitriles in a formal [3 + 2] dipolar cycloaddition reaction. Aliphatic, aromatic, and alpha,beta-unsaturated nitriles are excellent reaction partners, giving synthetically useful 2H-3,4-dihydropyrrole cycloaddition products in high yield.