methyl (E)-3-[(1S,3R,6S,7R,9S,12R,14R,15S,17R,19R)-6-[tert-butyl(dimethyl)silyl]oxy-6,12-dimethyl-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-7-yl]prop-2-enoate | 169895-69-6

• 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: methyl (E)-3-[(1S,3R,6S,7R,9S,12R,14R,15S,17R,19R)-6-[tert-butyl(dimethyl)silyl]oxy-6,12-dimethyl-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-7-yl]prop-2-enoate
• CAS: 169895-69-6
• 化学式: C₄₉H₉₄O₉Si₃
• 分子量: 911.536
• InChiKey: CYEMGWVEDCDEFI-HOXDECLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.83
• 重原子数：
  61
• 可旋转键数：
  19
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.94
• 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：

  methyl (E)-3-[(1S,3R,6S,7R,9S,12R,14R,15S,17R,19R)-6-[tert-butyl(dimethyl)silyl]oxy-6,12-dimethyl-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-7-yl]prop-2-enoate 在 palladium on activated charcoal lithium aluminium tetrahydride 、 正丁基锂 、 SO₂*pyridine 、 四丁基氟化铵 、 氢气 、 双氧水 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 22.5h， 生成 2-(((2R,4S,4aR,5aR,7aS,9R,10S,12aR,13aS,14aR)-10-((tert-butyldimethylsilyl)oxy)-9-((Z)-hexa-3,5-dien-1-yl)-5a,10-dimethyl-4-((triisopropylsilyl)oxy)hexadecahydrooxepino[3,2-b]pyrano[2',3':5,6]pyrano[2,3-f]oxepin-2-yl)methyl)acrylaldehyde
  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：

  叔丁基二甲硅基三氟甲磺酸酯 在 2,6-二甲基吡啶 、 臭氧 、 三苯基膦 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 26.0h， 生成 methyl (E)-3-[(1S,3R,6S,7R,9S,12R,14R,15S,17R,19R)-6-[tert-butyl(dimethyl)silyl]oxy-6,12-dimethyl-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-7-yl]prop-2-enoate
  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

• 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.