(+)-2(S)-methyl-2-(4-methyl-3-oxopentyl)cycloheptane-1,4-dione | 124764-75-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-2(S)-methyl-2-(4-methyl-3-oxopentyl)cycloheptane-1,4-dione
• 英文别名: (2S)-2-methyl-2-(4-methyl-3-oxopentyl)cycloheptane-1,4-dione
• CAS: 124764-75-6
• 化学式: C₁₄H₂₂O₃
• 分子量: 238.327
• InChiKey: CGLNYWZDKBTJDG-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.71
• 重原子数：
  17.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  51.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (+)-2(S)-methyl-2-(4-methyl-3-oxopentyl)cycloheptane-1,4-dione 在 氢氧化钾 、 氨 、 lithium 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 1.17h， 生成
  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：

  1-[(1S,3S)-1-methyl-2-methylidene-3-propan-2-ylcyclopentyl]but-3-en-2-ol 在 ruthenium(IV) oxide 、 sodium periodate 、 高氯酸 、 4 A molecular sieve 、 乙酸酐 、 pyridinium chlorochromate 作用下， 以 四氯化碳 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 2.42h， 生成 (+)-2(S)-methyl-2-(4-methyl-3-oxopentyl)cycloheptane-1,4-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;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：——