{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-methanol | 169895-49-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: {(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-methanol
• 英文别名: [(2S,3S)-2-methyl-3-[[(2R,3S,4S,6R)-4-phenylmethoxy-6-(3-phenylmethoxypropyl)-3-triethylsilyloxyoxan-2-yl]methyl]oxiran-2-yl]methanol
• CAS: 169895-49-2
• 化学式: C₃₃H₅₀O₆Si
• 分子量: 570.842
• InChiKey: AWWAKKCVDKEKRX-DNCBKPDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.66
• 重原子数：
  40
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  69.7
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  {(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-methanol 在 palladium on activated charcoal 4-二甲氨基吡啶 、 pyridine-SO3 complex 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 二甲基亚砜 、 苯 为溶剂， 反应 63.0h， 生成 3-[(2R,3S,4aR,6R,8S,8aS)-3-Acetoxy-8-hydroxy-6-(3-hydroxy-propyl)-2-methyl-octahydro-pyrano[3,2-b]pyran-2-yl]-propionic acid methyl 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
• 作为产物：
  描述：

  [(2R,3S,4S,6R)-2-Allyl-4-benzyloxy-6-(3-benzyloxy-propyl)-tetrahydro-pyran-3-yloxy]-triethyl-silane 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 L-(+)-酒石酸二乙酯 、 4 Angstroem MS 、 二异丁基氢化铝 、 臭氧 、 三苯基膦 作用下， 以 异辛烷 、 二氯甲烷 、 苯 为溶剂， 反应 15.5h， 生成 {(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-methanol
  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

• 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.