(+)-8-isopropyl-1(R)-methylbicyclo<5.3.0>dec-7(8)-en-5-one | 134031-74-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+)-8-isopropyl-1(R)-methylbicyclo<5.3.0>dec-7(8)-en-5-one
• 英文别名: (8aR)-8a-methyl-3-propan-2-yl-1,2,4,6,7,8-hexahydroazulen-5-one
• CAS: 134031-74-6
• 化学式: C₁₄H₂₂O
• 分子量: 206.328
• InChiKey: VLMOWSNYYOXYNL-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  (8aR)-8a-methyl-3-propan-2-yl-2,4,5,6,7,8-hexahydro-1H-azulen-5-ol 在 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以75%的产率得到(+)-8-isopropyl-1(R)-methylbicyclo<5.3.0>dec-7(8)-en-5-one
  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