(2R,3S,4aR,6R,8S,8aR)-2-(3-Hydroxy-propyl)-2-methyl-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-3-ol | 169895-56-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4aR,6R,8S,8aR)-2-(3-Hydroxy-propyl)-2-methyl-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-3-ol
• CAS: 169895-56-1
• 化学式: C₃₃H₆₈O₆Si₂
• 分子量: 617.07
• InChiKey: DEEHSKXBBMSQBC-HOEDGPACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.36
• 重原子数：
  41.0
• 可旋转键数：
  16.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.38
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,4aR,6R,8S,8aR)-2-(3-Hydroxy-propyl)-2-methyl-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-3-ol 在 potassium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (2R,3S,4aR,6R,8S,8aR)-3-Allyloxy-2-methyl-2-(3-triethylsilanyloxy-propyl)-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran
  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：

  (E)-3-[(2R,3S,4aR,6R,8S,8aS)-3-Acetoxy-8-benzyloxy-6-(3-benzyloxy-propyl)-2-methyl-octahydro-pyrano[3,2-b]pyran-2-yl]-acrylic acid methyl ester 在 palladium on activated charcoal 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 氢气 作用下， 以 甲醇 、 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.5h， 生成 (2R,3S,4aR,6R,8S,8aR)-2-(3-Hydroxy-propyl)-2-methyl-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-3-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

• 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.