(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-9-vinyl-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-8-ol | 169895-60-7

• 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: (2R,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-9-vinyl-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-8-ol
• 英文别名: (1R,3R,4S,6R,8R,10S,12R,13S)-12-ethenyl-1-methyl-4-tri(propan-2-yl)silyloxy-6-[3-tri(propan-2-yl)silyloxypropyl]-2,7,11-trioxatricyclo[8.5.0.03,8]pentadecan-13-ol
• CAS: 169895-60-7
• 化学式: C₃₆H₇₀O₆Si₂
• 分子量: 655.119
• InChiKey: MXJJYPXJMWYRBS-FJIWXNQSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.32
• 重原子数：
  44
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-9-vinyl-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-8-ol 在 palladium on activated charcoal 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 氢气 、 臭氧 、 三苯基膦 作用下， 以 吡啶 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 73.5h， 生成 2,2-Dimethyl-propionic acid 3-[(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-8-hydroxy-5a-methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-yl]-propyl ester
  参考文献：
  名称：

  Stereocontrolled Total Synthesis of Hemibrevetoxin B

  摘要：

  The stereocontrolled total synthesis of hemibrevetoxin B (1) has been achieved in 56 steps and 0.75% overall yield from D-mannose. The intramolecular reaction of gamma-alkoxyallylstannane with. aldehyde is a key step for the present total synthesis. Thus, the BF3. OEt2-mediated reaction of 24 gave 6 as a sole product. We encountered difficulty in the synthesis of gamma-alkoxyallylstannane 30 from the corresponding allyl ether 29 in which the gamma-alkoxy substituent became sterically quite bulky. This problem was solved by developing the acetal cleavage method for the synthesis of gamma-alkoxyallylstannanes. The cyclization of 38 proceeded smoothly to give the key intermediate 5 in a highly stereoselective manner. Construction of the alpha-vinyl aldehyde and (Z)-diene moieties were performed using Nicolaou's protocol.

  DOI：

  10.1021/jo9807619
• 作为产物：
  描述：

  3-[(2R,3S,4aR,6R,8S,8aR)-3-Allyloxy-2-methyl-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-2-yl]-propan-1-ol 在 pyridine-SO3 complex 、 四甲基乙二胺 、 三氟化硼乙醚 、 三丁基氯化锡 、 仲丁基锂 、 二甲基亚砜 、 三乙胺 作用下， 生成 (2R,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-9-vinyl-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-8-ol
  参考文献：
  名称：

  Total Synthesis of Hemibrevetoxin B

  摘要：

  The total synthesis of Hemibrevetoxin B is described. A new cyclization approach, based on the Lewis acid mediated intramolecular cyclization of the gamma-oxo-substituted allylic tin having an aldehyde group, produced the 6-6-7-7 polycyclic ether skeleton of the natural product with high stereoselectivity. The H-1 and C-13-NMR spectra of synthetic hemibrevetoxin B was identical with those of natural product.

  DOI：

  10.1016/00404-0399(50)10972-

文献信息

• Stereocontrolled Total Synthesis of Hemibrevetoxin B
  作者：Isao Kadota、Yoshinori Yamamoto

  DOI：10.1021/jo9807619

  日期：1998.9.1

  The stereocontrolled total synthesis of hemibrevetoxin B (1) has been achieved in 56 steps and 0.75% overall yield from D-mannose. The intramolecular reaction of gamma-alkoxyallylstannane with. aldehyde is a key step for the present total synthesis. Thus, the BF3. OEt2-mediated reaction of 24 gave 6 as a sole product. We encountered difficulty in the synthesis of gamma-alkoxyallylstannane 30 from the corresponding allyl ether 29 in which the gamma-alkoxy substituent became sterically quite bulky. This problem was solved by developing the acetal cleavage method for the synthesis of gamma-alkoxyallylstannanes. The cyclization of 38 proceeded smoothly to give the key intermediate 5 in a highly stereoselective manner. Construction of the alpha-vinyl aldehyde and (Z)-diene moieties were performed using Nicolaou's protocol.
• Total Synthesis of Hemibrevetoxin B
  作者：I Kadota

  DOI：10.1016/00404-0399(50)10972-

  日期：1995.8.7

  The total synthesis of Hemibrevetoxin B is described. A new cyclization approach, based on the Lewis acid mediated intramolecular cyclization of the gamma-oxo-substituted allylic tin having an aldehyde group, produced the 6-6-7-7 polycyclic ether skeleton of the natural product with high stereoselectivity. The H-1 and C-13-NMR spectra of synthetic hemibrevetoxin B was identical with those of natural product.