(1R,4R,6R)-(-)-1-methyl-4-(1-methylethenyl)-9-oxabicyclo[4.3.0]nonan-8-one | 171337-40-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (1R,4R,6R)-(-)-1-methyl-4-(1-methylethenyl)-9-oxabicyclo[4.3.0]nonan-8-one
• 英文别名: (3aR,5R,7aR)-7a-methyl-5-prop-1-en-2-yl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one
• CAS: 171337-40-9
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: INZZWOHUQRAAMD-CKYFFXLPSA-N

物化性质

• 熔点：
  62-64 °C
• 沸点：
  302.8±41.0 °C(predicted)
• 密度：
  1.030±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4R,6R)-(-)-1-methyl-4-(1-methylethenyl)-9-oxabicyclo[4.3.0]nonan-8-one 在 咪唑 、 甲醇 、 二甲基硫 、 sodium methylate 、 碳酸氢钠 、 臭氧 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 65.0h， 生成 (3aR,5R,7aR)-5-[tert-butyl(dimethyl)silyl]oxy-7a-methyl-3,3a,4,5,6,7-hexahydro-1-benzofuran-2-one
  参考文献：
  名称：

  Novel stereocontrolled synthesis of the tricyclic lactone (1R,3R,6R,9S)-6,9-dimethyl-8-oxo-7-oxatricyclo[4.3.0.03,9]nonane

  摘要：

  The stereocontrolled synthesis of (1R,3R,6R,9S)-6,9-dimethyl-s-oxo-7-oxatricyclo[4.3.0.0(3,9)]nonane 1 from (R)-(-)-carvone has been accomplished by application of a 13-step sequence with 12% overall yield. The absolute stereochemistry of the unsaturated acid 8a has been established by X-ray analysis of the chiral amide 8c. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00641-1
• 作为产物：
  描述：

  (+)-(1R,5R)-5-Isopropenyl-2-methylcyclohex-2-enylacetic acid 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 2.0h， 生成 (1R,4R,6R)-(-)-1-methyl-4-(1-methylethenyl)-9-oxabicyclo[4.3.0]nonan-8-one
  参考文献：
  名称：

  Novel stereocontrolled synthesis of the tricyclic lactone (1R,3R,6R,9S)-6,9-dimethyl-8-oxo-7-oxatricyclo[4.3.0.03,9]nonane

  摘要：

  The stereocontrolled synthesis of (1R,3R,6R,9S)-6,9-dimethyl-s-oxo-7-oxatricyclo[4.3.0.0(3,9)]nonane 1 from (R)-(-)-carvone has been accomplished by application of a 13-step sequence with 12% overall yield. The absolute stereochemistry of the unsaturated acid 8a has been established by X-ray analysis of the chiral amide 8c. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00641-1

文献信息

• Lactones. 9. Synthesis of Terpenoid LactonesActive Insect Antifeedants
  作者：Edyta Paruch、Zbigniew Ciunik、Jan Nawrot、Czesław Wawrzeńczyk

  DOI：10.1021/jf991307o

  日期：2000.10.1

  Claisen rearrangement and iodolactonization, four enantiomeric pairs of gamma-lactones were obtained. The structures of compounds were established by both spectroscopic and crystallographic methods. The lactones were tested for antifeeding activity toward grain storage pests-the granary weevil beetle (Sitophilus granarius L.), the khapra beetle (Trogoderma granarium Ev.), and the confused flour beetle (Tribolium

  从（+）-和（-）-紫苏醇开始，经克莱森重排和碘内酯化，获得了四个γ-内酯对映体对。化合物的结构通过光谱学和晶体学方法确定。测试了内酯对谷物储藏害虫-粮象鼻甲虫（Sitophilus granarius L.），khapra甲虫（Trogoderma granarium Ev。）和糊状的面粉甲虫（Tribolium confusum Duv。）的拒食活性。测试结果证明了（1R，4R，6R）-（-）-4-（1-甲基乙烯基）-9-氧杂双环[4.3.0] nonan-8-one（8a）及其对映异构体（ 8b）是针对所有上述测试物种的非常活跃的拒食剂。内酯8b也对桃-马铃薯蚜虫（Myzus persicae Sulz。）具有活性。活性取决于化合物手性中心的绝对构型。另外，内酯8a和8b的特征在于令人感兴趣的香料。
• Synthetic studies towards (+)-Dihydroampullicin. Michael addition of N-Boc-2-(tert-butyldimethylsiloxy)-3-methyl-pyrrole to α-methylene lactones
  作者：Isabel Marcos、Elena Redero、Francisco Bermejo

  DOI：10.1016/s0040-4039(00)01499-4

  日期：2000.10

  N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsiloxy)-3-methyl-pyrrole (4) to several α-methylene lactones catalyzed by fluoride ions yielded the corresponding homologated products (26–30) with good yields. Application of this reaction to the sililoxy bicyclic lactone (5) allowed us to isolate the tricyclic lactone (26), a highly valuable intermediate in our synthetic strategy leading to the growth

  的迈克尔加成ñ - （叔丁氧羰基）-2-（叔甲基甲硅烷氧基）-3-甲基吡咯（4）由氟离子催化的几个α亚甲基内酯得到相应的同系化的产品（26 - 30）具有良好的产量。该反应在甲硅烷氧​​基双环内酯（5）上的应用使我们能够分离出三环内酯（26），这是我们合成策略中非常有价值的中间体，可导致生长调节剂（+）-二氢氨苄青霉素（1）。
• Total synthesis of (−)-ampullicin and (+)-isoampullicin two growth regulators from Ampulliferina Sp. No. 27
  作者：Rosario Rico、Francisco Bermejo

  DOI：10.1016/0040-4039(95)01625-r

  日期：1995.10

  The growth regulators (-)-Ampullicin (1) and (+)-isoampullicin (2) have been synthesized utilizing carbaldehyde (25) as the chiral source and N-tertbutoxycarbonyl-3-methyl-2-(trimethylsiloxy)pyrrole (33) as the five-carbon homologative reagent. The synthesis of (1) and (2) is discussed in the context of retrosynthetic analysis. Carbaldehyde (25), has been prepared from both enantiomers of carvone, either (7) or (9), by application of a 15-step sequence with 4.7% and 5.4% overall yields respectively.