2-diazo-1-(2,5,5-trimethyl-4,6,7,8-tetrahydro-3H-chromen-2-yl)ethanone | 134312-42-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 2-diazo-1-(2,5,5-trimethyl-4,6,7,8-tetrahydro-3H-chromen-2-yl)ethanone
• CAS: 134312-42-8
• 化学式: C₁₄H₂₀N₂O₂
• 分子量: 248.325
• InChiKey: ISLHJDMSKVQOTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-diazo-1-(2,5,5-trimethyl-4,6,7,8-tetrahydro-3H-chromen-2-yl)ethanone 在 dirhodium tetraacetate 盐酸 、 sodium tetrahydroborate 、 三甲基氯硅烷 、 camphor-10-sulfonic acid 、 sodium iodide 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 51.75h， 生成 5,5,9-trimethylspiro<5.5>undec-8-en-1-one
  参考文献：
  名称：

  Intramolecular cyclopropanation-ring fragmentation leading to spirocyclic ring construction: a stereoselective synthesis of .beta.-chamigrene

  摘要：

  The transannular cyclopropanation of a keto carbene generated by Rh2(OAc)4 catalysis on a bicyclic dihydropyran nucleus provided a key oxatricyclic ketone intermediate for the synthesis of the [6.6] spirocyclic ring construction. Selective fragmentation of the cyclopropane followed by hydrolytic cleavage of the C-O bond provided the spirocyclic skeleton. Functional group manipulations to adjust oxidation states led to a total synthesis of (+/-)-beta-chamigrene in 14 steps without the use of protection/deprotection schemes.

  DOI：

  10.1021/jo00014a032
• 作为产物：
  描述：

  3,3-dimethyl-2-methylenecyclohexanone 在 sodium hydroxide 、 草酰氯 、 对苯二酚 作用下， 以 甲醇 、 苯 为溶剂， 反应 14.25h， 生成 2-diazo-1-(2,5,5-trimethyl-4,6,7,8-tetrahydro-3H-chromen-2-yl)ethanone
  参考文献：
  名称：

  Intramolecular cyclopropanation-ring fragmentation leading to spirocyclic ring construction: a stereoselective synthesis of .beta.-chamigrene

  摘要：

  The transannular cyclopropanation of a keto carbene generated by Rh2(OAc)4 catalysis on a bicyclic dihydropyran nucleus provided a key oxatricyclic ketone intermediate for the synthesis of the [6.6] spirocyclic ring construction. Selective fragmentation of the cyclopropane followed by hydrolytic cleavage of the C-O bond provided the spirocyclic skeleton. Functional group manipulations to adjust oxidation states led to a total synthesis of (+/-)-beta-chamigrene in 14 steps without the use of protection/deprotection schemes.

  DOI：

  10.1021/jo00014a032

文献信息

• ADAMS, JULIAN;LEPINE-FRENETTE, CAROLE;SPERO, DENICE M., J. ORG. CHEM., 56,(1991) N4, C. 4494-4498
  作者：ADAMS, JULIAN、LEPINE-FRENETTE, CAROLE、SPERO, DENICE M.

  DOI：——

  日期：——
• Intramolecular cyclopropanation-ring fragmentation leading to spirocyclic ring construction: a stereoselective synthesis of .beta.-chamigrene
  作者：Julian Adams、Carole Lepine-Frenette、Denice M. Spero

  DOI：10.1021/jo00014a032

  日期：1991.7

  The transannular cyclopropanation of a keto carbene generated by Rh2(OAc)4 catalysis on a bicyclic dihydropyran nucleus provided a key oxatricyclic ketone intermediate for the synthesis of the [6.6] spirocyclic ring construction. Selective fragmentation of the cyclopropane followed by hydrolytic cleavage of the C-O bond provided the spirocyclic skeleton. Functional group manipulations to adjust oxidation states led to a total synthesis of (+/-)-beta-chamigrene in 14 steps without the use of protection/deprotection schemes.