(+)-2-oxoisodauc-5-en-12-al | 125136-27-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-2-oxoisodauc-5-en-12-al
• 英文别名: (3R,3aS,8aS)-8a-methyl-8-oxo-3-propan-2-yl-1,2,3,3a,6,7-hexahydroazulene-5-carbaldehyde
• CAS: 125136-27-8
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: VYPYFZUEGQREKP-NFAWXSAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-2-oxoisodauc-5-en-12-al 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 甲醇 为溶剂， 以100%的产率得到(+)-aphanamol I
  参考文献：
  名称：

  Terpenoids to terpenoids: enantioselective construction of 5,6-, 5,7-, and 5,8-fused bicyclic systems. Application to the total synthesis of isodaucane sesquiterpenes and dolastane diterpenes

  摘要：

  The prevalence of a C12 common core (10) in C15-C30 terpenoids has been recognized. Construction of two ''chirons'' ((-)-11 and (-)-12a,b), corresponding to 10, from abundantly available (R)-(+)-limonene has been achieved through diastereoselective [3s.3s] sigmatropic processes 16 --> 11 and 19 --> 12, respectively. Chirons 11 and 12 have been successfully annulated to bicyclic hydrindanones 21, 23, and 30, hydrazulenoids 31-33, and 5,8-fused system 42 through methodologies that are short and practical. Thus, these enantiomerically pure bicyclics are available as advanced building blocks for higher terpene synthesis. One of the hydrazulenoids ((-)-31) has been elaborated to isodaucane sesquiterpenes (+)-aphanamol I (2) and (+)-2-oxoisodauc-5-en-12-al (46) through a novel restructuring protocol (31 --> 50). The stereo- and enantioselective synthesis reported here has established the absolute stereochemistry of isodaucane sesquiterpenes. The hydrazulenoid (-)-31 has also been deployed for the first enantioselective synthesis of oxygenated dolastane diterpenes (+)-isoamijiol (63) and (+)-dolasta-1(15),7,9-trien-14-ol (64). The key step in this venture was the stereoselective annulation of a six-membered ring through radical-induced alkyne-carbonyl cyclization (67 --> 68).

  DOI：

  10.1021/ja00015a034
• 作为产物：
  描述：

  (E)-4-methyl-pent-2-en-1-ol 在 selenium(IV) oxide 、 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 正丁基锂 、 Hoveyda-Grubbs catalyst second generation 、 十二/十四烷基二甲基氧化胺 、 potassium tert-butylate 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 双氧水 、 叔丁基锂 、 丙酸 、 二异丙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 正戊烷 为溶剂， 反应 108.34h， 生成 (+)-2-oxoisodauc-5-en-12-al
  参考文献：
  名称：

  硼亚烷基-烯烃环加成反应：在 Aphanamal 合成中的应用

  摘要：

  我们描述了亚烷基硼和未活化的烯烃之间不寻常的净[2+2]环加成反应。该反应为构建具有多功能有机硼酸酯的碳环系统提供了一种新方法。除了调查该反应的范围之外，我们还提供了有关该过程的机械基础的详细信息，并检查了其在天然产物 aphanamal 合成中的应用。

  DOI：

  10.1002/anie.201705720

文献信息

• MEHTA, GOVERDHAN;KRISHNAMURTHY, NACHARAJU;KARRA, SRINIVAS RAO, J. CHEM. SOC. CHEM. COMMUN.,(1989) N8, C. 1299-1300
  作者：MEHTA, GOVERDHAN、KRISHNAMURTHY, NACHARAJU、KARRA, SRINIVAS RAO

  DOI：——

  日期：——
• MEHTA, GOVERDHAN;KRISHNAMURTHY, NACHARAJU;RAO, KARRA SRINIVAS, J. AMER. CHEM. SOC., 113,(1991) N9, C. 5765-5775
  作者：MEHTA, GOVERDHAN、KRISHNAMURTHY, NACHARAJU、RAO, KARRA SRINIVAS

  DOI：——

  日期：——
• A Boron Alkylidene-Alkene Cycloaddition Reaction: Application to the Synthesis of Aphanamal
  作者：Xun Liu、T. Maxwell Deaton、Fredrik Haeffner、James P. Morken

  DOI：10.1002/anie.201705720

  日期：2017.9.11

  unusual net [2+2] cycloaddition reaction between boron alkylidenes and unactivated alkenes. This reaction provides a new method for the construction of carbocyclic ring systems bearing versatile organoboronic esters. Aside from surveying the scope of this reaction, we provide details about the mechanistic underpinnings of this process, and examine its application to the synthesis of the natural product

  我们描述了亚烷基硼和未活化的烯烃之间不寻常的净[2+2]环加成反应。该反应为构建具有多功能有机硼酸酯的碳环系统提供了一种新方法。除了调查该反应的范围之外，我们还提供了有关该过程的机械基础的详细信息，并检查了其在天然产物 aphanamal 合成中的应用。
• Terpenoids to terpenoids: enantioselective construction of 5,6-, 5,7-, and 5,8-fused bicyclic systems. Application to the total synthesis of isodaucane sesquiterpenes and dolastane diterpenes
  作者：Goverdhan Mehta、Nacharaju Krishnamurthy、Srinivas Rao Karra

  DOI：10.1021/ja00015a034

  日期：1991.7

  The prevalence of a C12 common core (10) in C15-C30 terpenoids has been recognized. Construction of two ''chirons'' ((-)-11 and (-)-12a,b), corresponding to 10, from abundantly available (R)-(+)-limonene has been achieved through diastereoselective [3s.3s] sigmatropic processes 16 --> 11 and 19 --> 12, respectively. Chirons 11 and 12 have been successfully annulated to bicyclic hydrindanones 21, 23, and 30, hydrazulenoids 31-33, and 5,8-fused system 42 through methodologies that are short and practical. Thus, these enantiomerically pure bicyclics are available as advanced building blocks for higher terpene synthesis. One of the hydrazulenoids ((-)-31) has been elaborated to isodaucane sesquiterpenes (+)-aphanamol I (2) and (+)-2-oxoisodauc-5-en-12-al (46) through a novel restructuring protocol (31 --> 50). The stereo- and enantioselective synthesis reported here has established the absolute stereochemistry of isodaucane sesquiterpenes. The hydrazulenoid (-)-31 has also been deployed for the first enantioselective synthesis of oxygenated dolastane diterpenes (+)-isoamijiol (63) and (+)-dolasta-1(15),7,9-trien-14-ol (64). The key step in this venture was the stereoselective annulation of a six-membered ring through radical-induced alkyne-carbonyl cyclization (67 --> 68).