3-[(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-8-Allyloxy-5a-methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-yl]-propan-1-ol | 169895-64-1

• 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: 3-[(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-8-Allyloxy-5a-methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-yl]-propan-1-ol
• 英文别名: 3-[(1R,3R,4S,6R,8R,10S,12R,13S)-1-methyl-13-prop-2-enoxy-4-tri(propan-2-yl)silyloxy-6-[3-tri(propan-2-yl)silyloxypropyl]-2,7,11-trioxatricyclo[8.5.0.03,8]pentadecan-12-yl]propan-1-ol
• CAS: 169895-64-1
• 化学式: C₄₀H₇₈O₇Si₂
• 分子量: 727.226
• InChiKey: GFYVGCWUAWTUAW-FSLMLJCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.12
• 重原子数：
  49
• 可旋转键数：
  19
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-[(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-8-Allyloxy-5a-methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-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 (1S,3R,6S,7R,9S,12R,14R,15S,17R,19R)-7-ethenyl-12-methyl-15-tri(propan-2-yl)silyloxy-17-[3-tri(propan-2-yl)silyloxypropyl]-2,8,13,18-tetraoxatetracyclo[10.8.0.03,9.014,19]icosan-6-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-
• 作为产物：
  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 、 amberlyst-15 、 氢气 、 potassium hydride 、 臭氧 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 吡啶 、 乙醚 、 乙醇 、 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 55.5h， 生成 3-[(2R,4S,4aR,5aR,8S,9R,10aS,11aR)-8-Allyloxy-5a-methyl-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-yl]-propan-1-ol
  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

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.