1-(3,3-dimethyl-2,4-dioxolanyl)-7-(1,1,2,2-tetramethyl-1-silapropoxy)hept-1-en-3-ol | 215810-53-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(3,3-dimethyl-2,4-dioxolanyl)-7-(1,1,2,2-tetramethyl-1-silapropoxy)hept-1-en-3-ol
• 英文别名: (E)-7-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]hept-1-en-3-ol
• CAS: 215810-53-0
• 化学式: C₁₈H₃₆O₄Si
• 分子量: 344.567
• InChiKey: JBSMAFGOAJSCQV-DXMKLJGBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-(3,3-dimethyl-2,4-dioxolanyl)-7-(1,1,2,2-tetramethyl-1-silapropoxy)hept-1-en-3-ol 在 4-二甲氨基吡啶 、 sodium periodate 、 重铬酸吡啶 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 溶剂黄146 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 73.5h， 生成 cholesteryl 5-hydroxy-8-oxooct-6-enoate
  参考文献：
  名称：

  Total Synthesis of γ-Hydroxy-α,β-Unsaturated Aldehydic Esters of Cholesterol and 2-Lysophosphatidylcholine

  摘要：

  Free radical-induced oxidation of polyunsaturated fatty esters in low-density lipoproteins (LDLs) generates 2-lysophosphatidylcholine (PC) and cholesterol esters of gamma-hydroxy-alpha,beta-unsaturated aldehydic acids that covalently modify LDL protein, and protein adducts of the corresponding acids are found in human blood. The chemistry and structures of these compounds resemble those of (E)-4-hydroxy-2-nonenal (HNE), previously considered the most cytotoxic aldehyde released during peroxidation of linoleate and arachidonate esters. The present report details total syntheses of 2-lyse-PC and cholesteryl esters of (E)-9-hydroxy-12-oxododec-10-enoic and (E)-5-hydroxy-8-oxooct-6-enoic acid that presumably are derived in vivo from linoleate and arachidonate esters, respectively. The syntheses depend on the use of a 3,3-dimethyl-2,4-dioxolanyl moiety as a latent aldehyde from which the chemically sensitive gamma-hydroxy-alpha,beta-unsaturated aldehyde array can be generated in the final step. For the cholesteryl esters, generation of the aldehyde group by oxidative cleavage of a vicinal diol could be accomplished in very good yields with periodate. However, for esters of 2-lyso-PC, the target aldehydes were not obtained upon treatment of vicinal diol precursors with periodate owing to a novel oxidative cleavage of the gamma-hydroxy-alpha,beta-unsaturated aldehydes by periodate. Fortunately, treatment of the vicinal diol precursors with Pb(OAc)(4) at -80 degrees C delivered good yields (82-85%) of the desired phospholipid aldehydes.

  DOI：

  10.1021/jo980861e
• 作为产物：
  描述：

  叔丁基(4-碘丁氧基)二甲基硅烷 、 (S,E)-3-(2,2-dimethyl-1,3-dioxolan-4-yl)acrylaldehyde 在 magnesium 作用下， 生成 1-(3,3-dimethyl-2,4-dioxolanyl)-7-(1,1,2,2-tetramethyl-1-silapropoxy)hept-1-en-3-ol
  参考文献：
  名称：

  Total Synthesis of γ-Hydroxy-α,β-Unsaturated Aldehydic Esters of Cholesterol and 2-Lysophosphatidylcholine

  摘要：

  Free radical-induced oxidation of polyunsaturated fatty esters in low-density lipoproteins (LDLs) generates 2-lysophosphatidylcholine (PC) and cholesterol esters of gamma-hydroxy-alpha,beta-unsaturated aldehydic acids that covalently modify LDL protein, and protein adducts of the corresponding acids are found in human blood. The chemistry and structures of these compounds resemble those of (E)-4-hydroxy-2-nonenal (HNE), previously considered the most cytotoxic aldehyde released during peroxidation of linoleate and arachidonate esters. The present report details total syntheses of 2-lyse-PC and cholesteryl esters of (E)-9-hydroxy-12-oxododec-10-enoic and (E)-5-hydroxy-8-oxooct-6-enoic acid that presumably are derived in vivo from linoleate and arachidonate esters, respectively. The syntheses depend on the use of a 3,3-dimethyl-2,4-dioxolanyl moiety as a latent aldehyde from which the chemically sensitive gamma-hydroxy-alpha,beta-unsaturated aldehyde array can be generated in the final step. For the cholesteryl esters, generation of the aldehyde group by oxidative cleavage of a vicinal diol could be accomplished in very good yields with periodate. However, for esters of 2-lyso-PC, the target aldehydes were not obtained upon treatment of vicinal diol precursors with periodate owing to a novel oxidative cleavage of the gamma-hydroxy-alpha,beta-unsaturated aldehydes by periodate. Fortunately, treatment of the vicinal diol precursors with Pb(OAc)(4) at -80 degrees C delivered good yields (82-85%) of the desired phospholipid aldehydes.

  DOI：

  10.1021/jo980861e

文献信息

• Total Synthesis of γ-Hydroxy-α,β-Unsaturated Aldehydic Esters of Cholesterol and 2-Lysophosphatidylcholine
  作者：Yijun Deng、Robert G. Salomon

  DOI：10.1021/jo980861e

  日期：1998.10.1

  Free radical-induced oxidation of polyunsaturated fatty esters in low-density lipoproteins (LDLs) generates 2-lysophosphatidylcholine (PC) and cholesterol esters of gamma-hydroxy-alpha,beta-unsaturated aldehydic acids that covalently modify LDL protein, and protein adducts of the corresponding acids are found in human blood. The chemistry and structures of these compounds resemble those of (E)-4-hydroxy-2-nonenal (HNE), previously considered the most cytotoxic aldehyde released during peroxidation of linoleate and arachidonate esters. The present report details total syntheses of 2-lyse-PC and cholesteryl esters of (E)-9-hydroxy-12-oxododec-10-enoic and (E)-5-hydroxy-8-oxooct-6-enoic acid that presumably are derived in vivo from linoleate and arachidonate esters, respectively. The syntheses depend on the use of a 3,3-dimethyl-2,4-dioxolanyl moiety as a latent aldehyde from which the chemically sensitive gamma-hydroxy-alpha,beta-unsaturated aldehyde array can be generated in the final step. For the cholesteryl esters, generation of the aldehyde group by oxidative cleavage of a vicinal diol could be accomplished in very good yields with periodate. However, for esters of 2-lyso-PC, the target aldehydes were not obtained upon treatment of vicinal diol precursors with periodate owing to a novel oxidative cleavage of the gamma-hydroxy-alpha,beta-unsaturated aldehydes by periodate. Fortunately, treatment of the vicinal diol precursors with Pb(OAc)(4) at -80 degrees C delivered good yields (82-85%) of the desired phospholipid aldehydes.