methyl (E)-3-[(2R,3S,4aR,6R,8S,8aS)-3-hydroxy-2-methyl-8-phenylmethoxy-6-(3-phenylmethoxypropyl)-4,4a,6,7,8,8a-hexahydro-3H-pyrano[3,2-b]pyran-2-yl]prop-2-enoate | 169895-52-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (E)-3-[(2R,3S,4aR,6R,8S,8aS)-3-hydroxy-2-methyl-8-phenylmethoxy-6-(3-phenylmethoxypropyl)-4,4a,6,7,8,8a-hexahydro-3H-pyrano[3,2-b]pyran-2-yl]prop-2-enoate
• CAS: 169895-52-7
• 化学式: C₃₀H₃₈O₇
• 分子量: 510.628
• InChiKey: YKQITCWYEUVRAP-XMIAAGEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-[(2R,3S,4aR,6R,8S,8aS)-3-hydroxy-2-methyl-8-phenylmethoxy-6-(3-phenylmethoxypropyl)-4,4a,6,7,8,8a-hexahydro-3H-pyrano[3,2-b]pyran-2-yl]prop-2-enoate 在 palladium on activated charcoal 、 palladium hydroxide - carbon RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 、 pyridine-SO3 complex 、 camphor-10-sulfonic acid 、 氢气 、 二甲基亚砜 、 三乙胺 、 2,4,6-trichlorobenzoyl chloride 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 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]propan-1-ol
  参考文献：
  名称：

  聚合半全毒素B的正式合成方法

  摘要：

  通过分子内α-氯乙酰氧基醚的烯丙基化和随后的闭环易位，实现了半短毒素B关键合成中间体的会聚合成。

  DOI：

  10.1016/j.tetlet.2006.11.058
• 作为产物：
  描述：

  (E)-3-{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-hydroxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-acrylic acid methyl ester 在 camphor-10-sulfonic acid 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 以81%的产率得到methyl (E)-3-[(2R,3S,4aR,6R,8S,8aS)-3-hydroxy-2-methyl-8-phenylmethoxy-6-(3-phenylmethoxypropyl)-4,4a,6,7,8,8a-hexahydro-3H-pyrano[3,2-b]pyran-2-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

• Formal Total Synthesis of Hemibrevetoxin B via the Intramolecular Allylation Followed by Ring-Closing Metathesis
  作者：Isao Kadota、Takashi Abe、Yukako Ishitsuka、Abeda S. Touchy、Ryoko Nagata、Yoshinori Yamamoto

  DOI：10.3987/com-07-s(w)39

  日期：——

  A formal total synthesis of hemibrevetoxin B (1) is described. Intramolecular allylation of α-chloroacetoxy ether 10, prepared from carboxylic acid 11 and alcohol 12, was carried out with MgBr 2 ·OEt 2 to give 27. Ring-closing metathesis of 27 furnished tetracycle 29, which was converted to a known synthetic intermediate 9, to complete a formal total synthesis of 1.

  描述了 hemibrevetoxin B (1) 的正式全合成。用 MgBr 2 ·OEt 2 对由羧酸 11 和醇 12 制备的 α-氯乙酰氧基醚 10 进行分子内烯丙基化，得到 27。 27 的闭环复分解得到四环 29，其转化为已知的合成中间体 9 ，完成1的正式全合成。
• 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.
• 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.
• A convergent approach to the formal total synthesis of hemibrevetoxin B
  作者：Isao Kadota、Takashi Abe、Yukako Ishitsuka、Abeda S. Touchy、Ryoko Nagata、Yoshinori Yamamoto

  DOI：10.1016/j.tetlet.2006.11.058

  日期：2007.1

  A convergent synthesis of the key synthetic intermediate of hemibrevetoxin B was achieved via the intramolecular allylation of an α-chloroacetoxy ether and subsequent ring-closing metathesis.

  通过分子内α-氯乙酰氧基醚的烯丙基化和随后的闭环易位，实现了半短毒素B关键合成中间体的会聚合成。