(3S,4S,5R,6R,E)-6-((dimethyl)(1,1-dimethylethyl)silyloxy)-3,5,7-trimethyl-8-(2-methyloxazol-4-yl)octa-1,7-dien-4-ol | 1403986-85-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (3S,4S,5R,6R,E)-6-((dimethyl)(1,1-dimethylethyl)silyloxy)-3,5,7-trimethyl-8-(2-methyloxazol-4-yl)octa-1,7-dien-4-ol
• 英文别名: (3S,4S,5R,6R,7E)-6-[tert-butyl(dimethyl)silyl]oxy-3,5,7-trimethyl-8-(2-methyl-1,3-oxazol-4-yl)octa-1,7-dien-4-ol
• CAS: 1403986-85-5
• 化学式: C₂₁H₃₇NO₃Si
• 分子量: 379.615
• InChiKey: ONHFFGOUPZYVIU-OMBJKEAHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  55.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,4S,5R,6R,E)-6-((dimethyl)(1,1-dimethylethyl)silyloxy)-3,5,7-trimethyl-8-(2-methyloxazol-4-yl)octa-1,7-dien-4-ol 在 copper(l) iodide 、 Hoveyda-Grubbs catalyst second generation 、 camphor-10-sulfonic acid 作用下， 以 甲醇 、 乙醚 、 1,2-二氯乙烷 为溶剂， 反应 3.0h， 生成 S-4-methylphenyl 2-((2R,3R,4S,5R,6R)-tetrahydro-4-hydroxy-3,5-dimethyl-6-((E)-1-(2-methyloxazol-4-yl)prop-1-en-2-yl)-2H-pyran-2-yl)ethanethioate
  参考文献：
  名称：

  Synthesis of the C20–C32 Tetrahydropyran Core of the Phorboxazoles and the C22 Epimer via a Stereodivergent Michael Reaction

  摘要：

  A stereoselective synthesis of the C20-C32 tetrahydropyran core of the phorboxazoles has been achieved in only seven steps and in a 31% overall yield. The C22 epimer was also synthesized. The key step was a silyl ether deprotection/oxy-Michael cyclization. When this step was conducted under Bronsted acid conditions, the C20-C32 core was formed with the desired 2,6-cis-stereochemistry. However, when the silyl ether deprotection/oxy-Michael cyclization was conducted under fluoride conditions buffered with acetic acid, the C22 epimer of the core was the sole product.

  DOI：

  10.1021/ol3026523
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 在 2,6-二甲基吡啶 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 23.25h， 生成 (3S,4S,5R,6R,E)-6-((dimethyl)(1,1-dimethylethyl)silyloxy)-3,5,7-trimethyl-8-(2-methyloxazol-4-yl)octa-1,7-dien-4-ol
  参考文献：
  名称：

  Synthesis of the C20–C32 Tetrahydropyran Core of the Phorboxazoles and the C22 Epimer via a Stereodivergent Michael Reaction

  摘要：

  A stereoselective synthesis of the C20-C32 tetrahydropyran core of the phorboxazoles has been achieved in only seven steps and in a 31% overall yield. The C22 epimer was also synthesized. The key step was a silyl ether deprotection/oxy-Michael cyclization. When this step was conducted under Bronsted acid conditions, the C20-C32 core was formed with the desired 2,6-cis-stereochemistry. However, when the silyl ether deprotection/oxy-Michael cyclization was conducted under fluoride conditions buffered with acetic acid, the C22 epimer of the core was the sole product.

  DOI：

  10.1021/ol3026523