methyl (5R,9S)-9-[tert-butyl(dimethyl)silyl]oxy-1-oxo-2-oxaspiro[4.5]dec-6-ene-6-carboxylate | 141510-39-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: methyl (5R,9S)-9-[tert-butyl(dimethyl)silyl]oxy-1-oxo-2-oxaspiro[4.5]dec-6-ene-6-carboxylate
• CAS: 141510-39-6
• 化学式: C₁₇H₂₈O₅Si
• 分子量: 340.492
• InChiKey: BBOXPWZDLNVMCB-YVEFUNNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  3-(p-tolylthio)-2-pyrone 在 2,6-二甲基吡啶 、 偶氮二异丁腈 、 三正丁基氢锡 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 150.08h， 生成 methyl (5R,9S)-9-[tert-butyl(dimethyl)silyl]oxy-1-oxo-2-oxaspiro[4.5]dec-6-ene-6-carboxylate
  参考文献：
  名称：

  Diels-Alder cycloadditions using nucleophilic 3-(p-tolylthio)-2-pyrone. Regiocontrolled and stereocontrolled synthesis of unsaturated, bridged, bicyclic lactones

  摘要：

  Captodative 3-(tolylthio)-2-pyrone (1) is shown to be reactive as a nucleophilic diene undergoing 2 + 4-cycloadditions with various electrophilic alkenes under sufficiently mild thermal conditions (less-than-or-equal-to 90-degrees-C) so that the initial bicyclic lactone adducts can be isolated on gram scale in moderate to very good yields (42-82%) without loss of CO2. These bicyclic adducts are formed regiospecifically and often with excellent stereoselectivity. These Diels-Alder cycloadditions are the first examples of a captodative unsaturated sulfide acting as an enophile. NMR data (C-13) are presented correlating the electron density in the pyrone diene systems with their Diels-Alder reactivity, and some transformations of the bicyclic lactone adducts are shown to illustrate the value and versatility of these richly functionalized synthetic intermediates.

  DOI：

  10.1021/jo00041a009

文献信息

• 3-bromo-2-pyrone: an easily prepared chameleon diene and a synthetic equivalent of 2-pyrone in thermal diels-alder cycloadditions
  作者：Gary H. Posner、Todd D. Nelson、Chris M. Kinter、Kamyar Afarinkia

  DOI：10.1016/s0040-4039(00)92368-2

  日期：1991.9

  3-Bromo-2-pyrone, a stable solid prepared by a new route (eq. 1), has been found to undergo smooth and regiospecific 2+4-cycloadditions between 78-90-degrees-C with both electron-rich and electron-deficient dienophiles; subsequent high-yield reductive debrominations produced halogen-free cycloadducts thus showing 3-bromo-2-pyrone to be a practical and effective synthetic equivalent of 2-pyrone in thermal Diels-Alder cycloadditions.