Acetic acid (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-yl ester | 169895-61-8

• 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: Acetic acid (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-yl ester
• CAS: 169895-61-8
• 化学式: C₃₈H₇₂O₇Si₂
• 分子量: 697.156
• InChiKey: BMSHASXNOVABCS-VOLKKHKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.89
• 重原子数：
  47.0
• 可旋转键数：
  15.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 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：

  Acetic acid (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-yl ester 在 palladium on activated charcoal lithium aluminium tetrahydride 、 氢气 、 臭氧 、 三乙胺 、 三苯基膦 作用下， 以 乙醚 、 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 34.5h， 生成 (2R,4S,4aR,5aR,8S,9R,10aS,11aR)-5a-Methyl-9-(3-triethylsilanyloxy-propyl)-4-triisopropylsilanyloxy-2-(3-triisopropylsilanyloxy-propyl)-dodecahydro-1,5,10-trioxa-cyclohepta[b]naphthalen-8-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
• 作为产物：
  描述：

  3-[(2R,3S,4aR,6R,8S,8aR)-2-Methyl-3-((Z)-3-tributylstannanyl-propenyloxy)-8-triisopropylsilanyloxy-6-(3-triisopropylsilanyloxy-propyl)-octahydro-pyrano[3,2-b]pyran-2-yl]-propan-1-ol 在 4-二甲氨基吡啶 、 pyridine-SO3 complex 、 三氟化硼乙醚 、 三乙胺 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 Acetic acid (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-yl 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

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.