(1S,7R,8R)-5-carbomethoxy-8-isopropyl-1-methylbicyclo<5.3.0>decane-2,6-dione 2-ethylene ketal | 125315-22-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,7R,8R)-5-carbomethoxy-8-isopropyl-1-methylbicyclo<5.3.0>decane-2,6-dione 2-ethylene ketal
• 英文别名: methyl (3'R,3'aR,8'aS)-8'a-methyl-4'-oxo-3'-propan-2-ylspiro[1,3-dioxolane-2,8'-2,3,3a,5,6,7-hexahydro-1H-azulene]-5'-carboxylate
• CAS: 125315-22-2；125409-69-0
• 化学式: C₁₈H₂₈O₅
• 分子量: 324.417
• InChiKey: BAMBYZYHKBYZFY-SHQMOOHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  23.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1S,7R,8R)-5-carbomethoxy-8-isopropyl-1-methylbicyclo<5.3.0>decane-2,6-dione 2-ethylene ketal 在 sodium tetrahydroborate 、 cerium(III) chloride 、 (COCl₂)2 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 苯 为溶剂， 反应 9.67h， 生成 (+)-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：

  (3S)-1-iriden-7-ol 在 ruthenium(IV) oxide 、 氢氧化钾 、 sodium periodate 、 正丁基锂 、 高氯酸 、 4 A molecular sieve 、 mercury(II) diacetate 、 氨 、 4-甲基苯磺酸吡啶 、 乙酸酐 、 lithium 、 六甲基二硅氮烷 、 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 、 苯 为溶剂， 反应 42.26h， 生成 (1S,7R,8R)-5-carbomethoxy-8-isopropyl-1-methylbicyclo<5.3.0>decane-2,6-dione 2-ethylene ketal
  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：——