(E)-3-{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-acrylic acid methyl ester | 169895-50-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-3-{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-acrylic acid methyl ester
• CAS: 169895-50-5
• 化学式: C₃₆H₅₂O₇Si
• 分子量: 624.89
• InChiKey: RUNHFQUZVXCBLK-VBKBFORMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.39
• 重原子数：
  44.0
• 可旋转键数：
  18.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  75.75
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (E)-3-{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-acrylic acid methyl ester 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以100%的产率得到(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
  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：

  (3aR,4R,6R,7aS)-4-Allyl-6-(3-benzyloxy-propyl)-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran 在 咪唑 、 titanium(IV) isopropylate 、 盐酸 、 叔丁基过氧化氢 、 pyridine-SO3 complex 、 L-(+)-酒石酸二乙酯 、 4 Angstroem MS 、 二异丁基氢化铝 、 二正丁基氧化锡 、 臭氧 、 三乙胺 、 三苯基膦 、 cesium fluoride 作用下， 以 甲醇 、 异辛烷 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 47.0h， 生成 (E)-3-{(2S,3S)-3-[(2R,3S,4S,6R)-4-Benzyloxy-6-(3-benzyloxy-propyl)-3-triethylsilanyloxy-tetrahydro-pyran-2-ylmethyl]-2-methyl-oxiranyl}-acrylic 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