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 | 169895-73-2

• 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: 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
• CAS: 169895-73-2
• 化学式: C₄₃H₇₆O₇Si₂
• 分子量: 761.243
• InChiKey: CRLYCZLGFVVKBA-YBGQHFAESA-N

物化性质

• 沸点：
  704.6±60.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  52.0
• 可旋转键数：
  14.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  72.45
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  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 在 silicon tetrafluoride 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.5h， 以76%的产率得到半短裸藻毒素B
  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,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-8-((Z)-3-tributylstannanyl-propenyloxy)-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-9-yl]-propan-1-ol 在 palladium on activated charcoal 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 正丁基锂 、 草酰氯 、 SO₂*pyridine 、 四丁基氟化铵 、 氢气 、 双氧水 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 臭氧 、 二甲基亚砜 、 三乙胺 、 三苯基膦 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 、 甲苯 、 苯 为溶剂， 反应 49.5h， 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

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.