(2E,4S,5S,6R,7R,8E)-S-p-tolyl 7-((dimethyl)(1,1-dimethylethyl)silyloxy)-5-hydroxy-4,6,8-trimethyl-9-(2-methyloxazol-4-yl)nona-2,8-dienethioate | 1403986-87-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 英文名称: (2E,4S,5S,6R,7R,8E)-S-p-tolyl 7-((dimethyl)(1,1-dimethylethyl)silyloxy)-5-hydroxy-4,6,8-trimethyl-9-(2-methyloxazol-4-yl)nona-2,8-dienethioate
• 英文别名: S-(4-methylphenyl) (2E,4S,5S,6R,7R,8E)-7-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4,6,8-trimethyl-9-(2-methyl-1,3-oxazol-4-yl)nona-2,8-dienethioate
• CAS: 1403986-87-7
• 化学式: C₂₉H₄₃NO₄SSi
• 分子量: 529.816
• InChiKey: SBIHNXRJIMJSTE-VJRBKWGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.59
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  97.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2E,4S,5S,6R,7R,8E)-S-p-tolyl 7-((dimethyl)(1,1-dimethylethyl)silyloxy)-5-hydroxy-4,6,8-trimethyl-9-(2-methyloxazol-4-yl)nona-2,8-dienethioate 在 camphor-10-sulfonic acid 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 以20%的产率得到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 、 copper(l) iodide 、 Hoveyda-Grubbs catalyst second generation 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 26.25h， 生成 (2E,4S,5S,6R,7R,8E)-S-p-tolyl 7-((dimethyl)(1,1-dimethylethyl)silyloxy)-5-hydroxy-4,6,8-trimethyl-9-(2-methyloxazol-4-yl)nona-2,8-dienethioate
  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

文献信息

• Synthesis of the C20–C32 Tetrahydropyran Core of the Phorboxazoles and the C22 Epimer via a Stereodivergent Michael Reaction
  作者：Paul A. Clarke、Kristaps Ermanis

  DOI：10.1021/ol3026523

  日期：2012.11.2

  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.