cis-cyclohex-2-ene-1,4-diol bis-trimethylsilyl ether | 142532-53-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: cis-cyclohex-2-ene-1,4-diol bis-trimethylsilyl ether
• 英文别名: cis-bis-O-trimethylsilylcyclohex-2-ene-1,4-diol；trimethyl-[(1S,4R)-4-trimethylsilyloxycyclohex-2-en-1-yl]oxysilane
• CAS: 142532-53-4
• 化学式: C₁₂H₂₆O₂Si₂
• 分子量: 258.508
• InChiKey: NSQAEKNTGNBTDU-TXEJJXNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  cis-cyclohex-2-ene-1,4-diol bis-trimethylsilyl ether 在 4-二甲氨基吡啶 、 碳酸氢钠 、 间氯过氧苯甲酸 、 N,N'-二环己基碳二亚胺 、 柠檬酸 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 反应 13.3h， 生成 c-3-<3-(tert-butyldiphenylsilyloxy)prop-1-ynyl>-1-O-phenylacetyl-2-O-(p-tolylsulfonyl)-4-O-trimethylsilylcyclohexane-r-1,t-2,c-4-triol
  参考文献：
  名称：

  The stereoselective synthesis of 2,9,10-trioxatricyclo[4.3.1.0]decane analogues of resiniferatoxin

  摘要：

  以环己烷-1,3-二烯为原料，立体选择性地合成了具有 2,9,10-三氧杂三环[4.3.1.0]癸烷系统的二萜树脂藜芦毒素的结构简化类似物。

  DOI：

  10.1039/c39910000215
• 作为产物：
  描述：

  1,3-环己二烯 在 tetraphenylporphyrin 氧气 、 三乙胺 、 硫脲 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 29.5h， 生成 cis-cyclohex-2-ene-1,4-diol bis-trimethylsilyl ether
  参考文献：
  名称：

  Synthesis of 2,9,10-trioxatricyclo[4.3.1.0]decane analogues of resiniferatoxin

  摘要：

  Structurally simplified analogues of the daphnane diterpene resiniferatoxin (RTX) 1, possessing the unusual 2,9,10-trioxatricyclo[4.3.1.0 3,8]decane system have been synthesised stereoselectively from cyclohexa-1,3-diene: functionalisation of the diene afforded the anti-epoxide, 1,4-di-O-benzyl-t-2,t-3-epoxycyclohexane-r-1,c-4-diol 4, the ring-opening of which was examined using various organometallic reagents; organoaluminium species were found to be the most efficient to effect this reaction. When trimethylsilyl (in place of benzyl) ethers were used to protect the diol, selective deprotection of 1,4-di-O-trimethylsilyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 16 was achieved using citric acid in methanol - the equatorially disposed trimethylsilyl ether was found to be more easily cleaved than the axially orientated one. Formation of the tricyclic orthoester was achieved by the generation of a dioxolenium ion from 1-O-phenylacetyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 19, by heating in 2,4,6-trimethylpyridine, with in situ intramolecular trapping by the suitably orientated hydroxy group to give 1-benzyl-7-(3-tert-butyldiphenylsilyloxyprop-1-ynyl)-2,9,10-trioxatricyclo[4.3.1.0 3,8]decane 20.

  DOI：

  10.1039/p19920001229

文献信息

• The stereoselective synthesis of 2,9,10-trioxatricyclo[4.3.1.0]decane analogues of resiniferatoxin
  作者：Graham C. Bloomfield、Roger Wrigglesworth、Timothy J. Ritchie

  DOI：10.1039/c39910000215

  日期：——

  Structurally simplified analogues of the diterpene resiniferatoxin possessing a 2,9,10-trioxatricyclo[4.3.1.0]decane system are synthesised stereoselectively from cyclohexa-1,3-diene.

  以环己烷-1,3-二烯为原料，立体选择性地合成了具有 2,9,10-三氧杂三环[4.3.1.0]癸烷系统的二萜树脂藜芦毒素的结构简化类似物。
• Synthesis of 2,9,10-trioxatricyclo[4.3.1.0]decane analogues of resiniferatoxin
  作者：Graham C. Bloomfield、Timothy J. Ritchie、Roger Wrigglesworth

  DOI：10.1039/p19920001229

  日期：——

  Structurally simplified analogues of the daphnane diterpene resiniferatoxin (RTX) 1, possessing the unusual 2,9,10-trioxatricyclo[4.3.1.0 3,8]decane system have been synthesised stereoselectively from cyclohexa-1,3-diene: functionalisation of the diene afforded the anti-epoxide, 1,4-di-O-benzyl-t-2,t-3-epoxycyclohexane-r-1,c-4-diol 4, the ring-opening of which was examined using various organometallic reagents; organoaluminium species were found to be the most efficient to effect this reaction. When trimethylsilyl (in place of benzyl) ethers were used to protect the diol, selective deprotection of 1,4-di-O-trimethylsilyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 16 was achieved using citric acid in methanol - the equatorially disposed trimethylsilyl ether was found to be more easily cleaved than the axially orientated one. Formation of the tricyclic orthoester was achieved by the generation of a dioxolenium ion from 1-O-phenylacetyl-2-O-(p-tolylsulfonyl)-c-3-[3-(tert-butyldiphenylsilyloxy)-prop-1-ynyl]cyclohexane-r-1,t-2,c-4-triol 19, by heating in 2,4,6-trimethylpyridine, with in situ intramolecular trapping by the suitably orientated hydroxy group to give 1-benzyl-7-(3-tert-butyldiphenylsilyloxyprop-1-ynyl)-2,9,10-trioxatricyclo[4.3.1.0 3,8]decane 20.