(9-Butyl-3,3-dimethyl-1,5-dioxo-2,4-dioxa-7-azaspiro[5.5]undec-9-en-7-yl) 4-methylbenzenesulfonate | 1027940-16-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (9-Butyl-3,3-dimethyl-1,5-dioxo-2,4-dioxa-7-azaspiro[5.5]undec-9-en-7-yl) 4-methylbenzenesulfonate
• CAS: 1027940-16-4
• 化学式: C₂₁H₂₇NO₇S
• 分子量: 437.514
• InChiKey: HMXPRGRICLDQFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (9-Butyl-3,3-dimethyl-1,5-dioxo-2,4-dioxa-7-azaspiro[5.5]undec-9-en-7-yl) 4-methylbenzenesulfonate 在 lithium hydroxide 、 N-氯代丁二酰亚胺 、 水 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 16.0h， 生成 5-丁基吡啶-2-羧酸
  参考文献：
  名称：

  Synthesis of Substituted Pyridines via Regiocontrolled [4 + 2] Cycloadditions of Oximinosulfonates

  摘要：

  Diels-Alder cycloadditions of oximinosulfonate 8 with a variety of 1,3-dienes proceed with regiochemistry opposite to that observed with conventional imino dienophiles, providing expeditious synthetic routes to substituted pyridines, tetrahydropyridines, and pyrrolines. The oximinosulfonate 8 is prepared in one convenient synthetic operation from Meldrum's acid and reacts with conjugated dienes at -78 degrees C in the presence of 2 equiv of dimethylaluminum chloride to afford [4 + 2] cycloadducts in good to excellent yield. Exposure of these cycloadducts to the action of NaOMe and N-chlorosuccinimide in methanol-THF at room temperature then produces substituted pyridines. The utility of this new two-step annulation protocol is demonstrated in total syntheses of the pyridine alkaloids fusaric acid and (S)-(+)-fusarinolic acid. Heating the [4 + 2] cycloadducts derived from 8 in a mixture of acetonitrile and pH 7 phosphate buffer induces an unusual Stieglitz-type rearrangement leading to the formation of interesting spirobicyclic pyrrolines.

  DOI：

  10.1021/jo981014e
• 作为产物：
  描述：

  对甲苯磺酰氯 在 二甲基氯化铝 、 sodium nitrite 作用下， 以 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 2.55h， 生成 (9-Butyl-3,3-dimethyl-1,5-dioxo-2,4-dioxa-7-azaspiro[5.5]undec-9-en-7-yl) 4-methylbenzenesulfonate
  参考文献：
  名称：

  PREPARATION OF SUBSTITUTED PYRIDINES VIA REGIOCONTROLLED [4 + 2] CYCLOADDITIONS OF OXIMINOSULFONATES: METHYL 5-METHYLPYRIDINE-2-CARBOXYLATE

  摘要：

  DOI：

  10.15227/orgsyn.080.0133

文献信息

• Synthesis of Substituted Pyridines via Regiocontrolled [4 + 2] Cycloadditions of Oximinosulfonates
  作者：Adam R. Renslo、Rick L. Danheiser

  DOI：10.1021/jo981014e

  日期：1998.10.1

  Diels-Alder cycloadditions of oximinosulfonate 8 with a variety of 1,3-dienes proceed with regiochemistry opposite to that observed with conventional imino dienophiles, providing expeditious synthetic routes to substituted pyridines, tetrahydropyridines, and pyrrolines. The oximinosulfonate 8 is prepared in one convenient synthetic operation from Meldrum's acid and reacts with conjugated dienes at -78 degrees C in the presence of 2 equiv of dimethylaluminum chloride to afford [4 + 2] cycloadducts in good to excellent yield. Exposure of these cycloadducts to the action of NaOMe and N-chlorosuccinimide in methanol-THF at room temperature then produces substituted pyridines. The utility of this new two-step annulation protocol is demonstrated in total syntheses of the pyridine alkaloids fusaric acid and (S)-(+)-fusarinolic acid. Heating the [4 + 2] cycloadducts derived from 8 in a mixture of acetonitrile and pH 7 phosphate buffer induces an unusual Stieglitz-type rearrangement leading to the formation of interesting spirobicyclic pyrrolines.
• PREPARATION OF SUBSTITUTED PYRIDINES VIA REGIOCONTROLLED [4 + 2] CYCLOADDITIONS OF OXIMINOSULFONATES: METHYL 5-METHYLPYRIDINE-2-CARBOXYLATE
  作者：Danheiser, Rick L.、Renslo, Adam R.、Amos, David T.、Wright, Graham T.、Krause, Helga、Fürstner, Alois

  DOI：10.15227/orgsyn.080.0133

  日期：——