(2E,4E)-6-[(2S,4R,5R,6R)-6-[(2R,5S,6E,9R,11R,12E)-14-[(4S,5R,6S)-2,2-ditert-butyl-5-methyl-6-[(2S)-1-tri(propan-2-yl)silyloxypropan-2-yl]-1,3,2-dioxasilinan-4-yl]-5,11-dimethoxy-6,9-dimethyltetradeca-6,12-dien-2-yl]-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]hexa-2,4-dienal | 210709-28-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (2E,4E)-6-[(2S,4R,5R,6R)-6-[(2R,5S,6E,9R,11R,12E)-14-[(4S,5R,6S)-2,2-ditert-butyl-5-methyl-6-[(2S)-1-tri(propan-2-yl)silyloxypropan-2-yl]-1,3,2-dioxasilinan-4-yl]-5,11-dimethoxy-6,9-dimethyltetradeca-6,12-dien-2-yl]-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]hexa-2,4-dienal
• CAS: 210709-28-7
• 化学式: C₆₀H₁₀₄O₉Si₂
• 分子量: 1025.65
• InChiKey: FIKJOLZRRXJTOQ-JUWDSPFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.86
• 重原子数：
  71
• 可旋转键数：
  29
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  90.9
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2E,4E)-6-[(2S,4R,5R,6R)-6-[(2R,5S,6E,9R,11R,12E)-14-[(4S,5R,6S)-2,2-ditert-butyl-5-methyl-6-[(2S)-1-tri(propan-2-yl)silyloxypropan-2-yl]-1,3,2-dioxasilinan-4-yl]-5,11-dimethoxy-6,9-dimethyltetradeca-6,12-dien-2-yl]-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]hexa-2,4-dienal 在 sodium chlorite 、 sodium dihydrogenphosphate 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 吡啶 、 水 、 叔丁醇 为溶剂， 反应 18.0h， 生成 (2E,4E)-6-[(2S,4R,5R,6R)-6-((5E,11E)-(1R,4S,8R,10R,14S,15R,16S,17S)-14,16-Dihydroxy-4,10-dimethoxy-1,5,8,15,17-pentamethyl-18-triisopropylsilanyloxy-octadeca-5,11-dienyl)-2-(4-methoxy-phenyl)-5-methyl-[1,3]dioxan-4-yl]-hexa-2,4-dienoic acid
  参考文献：
  名称：

  Studies in marine macrolide synthesis: Construction of a 24-membered macrocyclic intermediate for aplyronine A

  摘要：

  The C-1-C-27 macrolide 2, which contains 11 stereocentres and 4 double bonds, was constructed by an efficient 3-component coupling followed by a macrolactonisation/isomerization sequence. Key steps were the alkylation of the dianion of phosphonate 5 with iodide 7 and a Ba(OH)(2)-mediated HWE reaction with 6 to install the trisubstituted double bond. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01192-7
• 作为产物：
  描述：

  tert-Butyl-{(2E,4E)-6-[(2S,4R,5R,6S)-6-((S)-2-iodo-1-methyl-ethyl)-2-(4-methoxy-phenyl)-5-methyl-[1,3]dioxan-4-yl]-hexa-2,4-dienyloxy}-dimethyl-silane 在 六甲基磷酰三胺 、 barium dihydroxide 、 正丁基锂 、 dimethyl sulfide borane 、 (R)-proline derived oxazaborolidine 、 pH₇ buffer 、 sodium hydride 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 10.5h， 生成 (2E,4E)-6-[(2S,4R,5R,6R)-6-[(2R,5S,6E,9R,11R,12E)-14-[(4S,5R,6S)-2,2-ditert-butyl-5-methyl-6-[(2S)-1-tri(propan-2-yl)silyloxypropan-2-yl]-1,3,2-dioxasilinan-4-yl]-5,11-dimethoxy-6,9-dimethyltetradeca-6,12-dien-2-yl]-2-(4-methoxyphenyl)-5-methyl-1,3-dioxan-4-yl]hexa-2,4-dienal
  参考文献：
  名称：

  Studies in marine macrolide synthesis: Construction of a 24-membered macrocyclic intermediate for aplyronine A

  摘要：

  The C-1-C-27 macrolide 2, which contains 11 stereocentres and 4 double bonds, was constructed by an efficient 3-component coupling followed by a macrolactonisation/isomerization sequence. Key steps were the alkylation of the dianion of phosphonate 5 with iodide 7 and a Ba(OH)(2)-mediated HWE reaction with 6 to install the trisubstituted double bond. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01192-7

文献信息

• A Facile Oxidation/Deprotection of Electron Rich Silyl Ethers Using DDQ
  作者：Ian Paterson、Cameron J. Cowden、Volker S. Rahn、Michael D. Woodrow

  DOI：10.1055/s-1998-1810

  日期：1998.8

  The selective oxidation/deprotection of allylic and benzylic silyl ethers to give aldehydes can be achieved by hydride abstraction with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under neutral conditions. This reaction is possible in the presence of a variety of silyl protecting groups, as in 2 → 3, and even PMB ethers and PMP acetals, as in 14 → 15, which are normally labile under DDQ oxidation

  烯丙基和苄基甲硅烷基醚的选择性氧化/脱保护生成醛可以通过在中性条件下用 2,3-二氯-5,6-二氰基-1,4-苯醌 (DDQ) 进行氢化物提取来实现。在存在各种甲硅烷基保护基团（如 2 → 3），甚至 PMB 醚和 PMP 缩醛（如 14 → 15）的情况下，该反应是可能的，它们通常在 DDQ 氧化条件下不稳定。
• Studies in marine macrolide synthesis: Construction of a 24-membered macrocyclic intermediate for aplyronine A
  作者：Ian Paterson、Michael D Woodrow、Cameron J Cowden

  DOI：10.1016/s0040-4039(98)01192-7

  日期：1998.8

  The C-1-C-27 macrolide 2, which contains 11 stereocentres and 4 double bonds, was constructed by an efficient 3-component coupling followed by a macrolactonisation/isomerization sequence. Key steps were the alkylation of the dianion of phosphonate 5 with iodide 7 and a Ba(OH)(2)-mediated HWE reaction with 6 to install the trisubstituted double bond. (C) 1998 Elsevier Science Ltd. All rights reserved.