α-himachalene | 66537-34-6

• 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: α-himachalene
• 英文别名: α-Himachalen；(4aR,9aS)-3,5,5-trimethyl-9-methylidene-2,4a,6,7,8,9a-hexahydro-1H-benzo[7]annulene
• CAS: 66537-34-6
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: ZJSIKVDEOWWVEH-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  diethyl (3Z,8E)-6-(3-triethylsilyloxy-7,7,10-trimethyl-1,3,8,10-undecatetraenyl)phosphate 在 吡啶 、 potassium fluoride 、 lithium 、 乙胺 、 叔丁醇 、 三氯氧磷 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 苯 为溶剂， 反应 22.25h， 生成 α-himachalene
  参考文献：
  名称：

  A Convergent Synthesis of (�)-?- and ?-Himachalenes

  摘要：

  Abstract(±)‐α and β‐Himachalene, 5 and 6, have been synthesized in a convergent manner from 3,3‐dimethylacrolein (9), the ester enolate 10 and the silyloxypentadienyllithium 7. The key steps are the regioselective γ‐addition of the dienal 13 to 7 and the intramolecular Diels‐Alder addition 15 → 16. Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6.

  DOI：

  10.1002/hlca.19810640815

文献信息

• Photoinduced molecular transformations. Part 150. A new total synthesis of (±)-α-Himachalene based on a Sequence involving [2+2] photoaddition and regioselective β-scission of alkoxyl radicals generated from the resulting cyclobutanols
  作者：Hiroshi Suginome、Yutaka Nakayama

  DOI：10.1016/s0040-4020(01)85261-3

  日期：1994.1

  A new total synthesis of α-himachalene, a sesquiterpene isolated from essential oil of a Himalayan cedar (Cedrus deodara Loud),has been achieved. It is based on a sequence involving the [2+2] photoaddition of a cyclic enone with a silyl enol ether, followed by a radical-induced ring expansion of the resulting fused cyclobutanol; the [2+2] photoaddition of cyclohexenone with 1-methyl-2-trimethylsiloxy-1-cyclopentene

  从喜马拉雅雪松（Cedrus deodara Loud）的香精油中分离得到的倍半萜烯-倍半萜烯已经完成了新的全合成。它基于一个序列，该序列涉及将环烯酮与甲硅烷基烯醇醚进行[2 + 2]光加成，然后自由基诱导所得稠合的环丁醇环扩环；环己烯酮与1-甲基-2-三甲基甲硅烷氧基-1-环戊烯在苯中的[2 + 2]光加成反应，然后用酸处理所得的光加合物，得到2-羟基-6-甲基三环[5.4.0.0]的立体异构体混合物2,6 [十一碳六烯-8]（33％）伴随有同分异构的光加合物的逆醛醇缩合反应生成的产物（27％）。前者转化为8-叔丁基二甲基甲硅烷氧基-6-甲基三环[5.4.0.0 2,6通过3个步骤完成undecan-2-ol 。由这种受保护的稠合环丁醇在苯中辐照生成的次碘酸盐导致β环稠合键断裂，得到官能化的双环[5.4.0]十一烷的混合物，该混合物转变为顺式-6,6-二甲基-8 -羟基双环[5.4.0]
• A diastereoselective synthesis of (1SR,3SR,7RS)-3-methyl-α-himachalene, the sex pheromone of the sandfly, Lutzomyia longipalpis (Diptera: Psychodidae)
  作者：Samuel Dufour、Pascalie Castets、John A. Pickett、Antony M. Hooper

  DOI：10.1016/j.tet.2012.04.037

  日期：2012.6

  The sandfly, Lutzomyia longipalpis, vectors the causative agent of visceral leishmaniasis in the New World. The male-produced pheromone, (1S,3S,7R)-3-methyl-alpha-himachalene provides an opportunity for pest managing this pest problem by influencing the behaviour of the biting female. Previous syntheses of the pheromone have all focused on a late stage Diels-Alder cyclisation to generate the bicyclic cis-himachalene skeleton. By adopting a new retrosynthetic analysis that depends on an early stage Diels-Alder cyclisation, the number of steps has been reduced to ten, of which five are catalytic and so provides access to quantities suitable for field-scale experiments. (C) 2012 Elsevier Ltd. All rights reserved.
• Liu, Hsing-Jang; Browne, Eric N. C., Canadian Journal of Chemistry, 1981, vol. 59, p. 601 - 608
  作者：Liu, Hsing-Jang、Browne, Eric N. C.

  DOI：——

  日期：——
• A Convergent Synthesis of (�)-?- and ?-Himachalenes
  作者：Wolfgang Oppolzer、Roger L. Snowden

  DOI：10.1002/hlca.19810640815

  日期：1981.12.16

  Abstract(±)‐α and β‐Himachalene, 5 and 6, have been synthesized in a convergent manner from 3,3‐dimethylacrolein (9), the ester enolate 10 and the silyloxypentadienyllithium 7. The key steps are the regioselective γ‐addition of the dienal 13 to 7 and the intramolecular Diels‐Alder addition 15 → 16. Hydrogenolysis of the diethylphosphate group and functionalization at C (5) completed the synthesis of 5 and 6.