(+)-8-isopropyl-1(S)-methylbicyclo<5.3.0>dec-7-ene-2,6-dione | 125315-19-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-8-isopropyl-1(S)-methylbicyclo<5.3.0>dec-7-ene-2,6-dione
• 英文别名: (8aS)-8a-methyl-3-propan-2-yl-2,5,6,7-tetrahydro-1H-azulene-4,8-dione
• CAS: 125315-19-7
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: REPYDWPWFLGRLG-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+)-8-isopropyl-1(S)-methylbicyclo<5.3.0>dec-7-ene-2,6-dione 在 palladium on activated charcoal 甲醇 、 氢气 、 sodium 作用下， 以 乙酸乙酯 为溶剂， 30.0 ℃ 、172.37 kPa 条件下， 反应 13.0h， 生成 (-)-(1S,7S,8S)-8-isopropyl-1-methylbicyclo<5.3.0>decane-2,6-dione
  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：

  (3S)-1-iriden-7-ol 在 ruthenium(IV) oxide 、 氢氧化钾 、 sodium periodate 、 高氯酸 、 4 A molecular sieve 、 mercury(II) diacetate 、 乙酸酐 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 25.42h， 生成 (+)-8-isopropyl-1(S)-methylbicyclo<5.3.0>dec-7-ene-2,6-dione
  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

文献信息

• Enantioselective approach to isodaucane sesquiterpenes. Total synthesis of (+)-aphanamol-I and (+)-2-oxo-isodauc-5-en-12-al
  作者：Goverdhan Mehta、Nacharaju Krishnamurthy、Srinivas Rao Karra

  DOI：10.1039/c39890001299

  日期：——

  A general approach to isodaucane sesquiterpenes from (R)-(+)-limonene, resulting in the total synthesis of (+)-aphanamol-I (3) and (+)-2-oxo-isodauc-5-en-12-al (5), is described.

  从（R）-（+）-柠檬烯制异七烷倍半萜的通用方法，导致（+）-甲氨酚-I（3）和（+）-2-氧代-异豆基-5-烯-12-的全合成描述了al（5）。
• Mehta, Goverdhan; Karra, Srinivasa Rao, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1989, vol. 28, # 1-11, p. 367 - 368
  作者：Mehta, Goverdhan、Karra, Srinivasa Rao

  DOI：——

  日期：——
• 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;KARRA, SRINIVASA RAO, INDIAN J. CHEM. B, 28,(1989) N, C. 367-368
  作者：MEHTA, GOVERDHAN、KARRA, SRINIVASA 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：——