(5R)-2-methylidene-5-isopropylcyclohexanone | 93215-97-5

• 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: (5R)-2-methylidene-5-isopropylcyclohexanone
• 英文别名: (+)-(4R)-1(7)-p-menthen-2-one；α-santolinenone；(5R)-2-methylidene-5-propan-2-ylcyclohexan-1-one
• CAS: 93215-97-5
• 化学式: C₁₀H₁₆O
• 分子量: 152.236
• InChiKey: QIHBCMQXRORFNY-SECBINFHSA-N

物化性质

• 沸点：
  225.2±10.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (5R)-2-methylidene-5-isopropylcyclohexanone 在 palladium diacetate 、 四(三苯基膦)钯 、 cerium(III) chloride 、 三丁基膦 、 diethylzinc 、 苯基锂 作用下， 以 四氢呋喃 、 乙醚 、 环己烷 、 溶剂黄146 为溶剂， 反应 35.5h， 生成 (1R,5R,9R)-1-(but-3-enyl)-9-isopropyl-6-methylidenespiro[4.5]decane
  参考文献：
  名称：

  Synthesis of (−)-Erythrodiene and (+)-7-Epispirojatamolvia Intramolecular Pd-Catalyzed Allylzincation

  摘要：

  Two spirobicyclic sesquiterpenoids, (-)-erythrodiene (1) and (+)-7-epispirojatamol (30),were synthesized in enantiomerically pure form via an intramolecular allylzincation process. The allylzinc species were formed in the presence of Et,Zn via transmetallation of a catalytically generated allylpalladium intermediate. Several Pd catalysts were tested for this transformation, and [Pd(OAc)(2)/Bu3P(1 equiv.) was found to be, by far, the most effective. Whereas the preparation of 1 involved allylzincation of a tethered terminal olefin. 30 was formed via a novel intramolecular allylzincation of a methyl ketone. Both reactions showed the same stereochemical preference. yielding the spirobicyclic products in 95:5 and 4:1 diastereoisomer ratios, respectively.

  DOI：

  10.1002/1522-2675(20010228)84:2<416::aid-hlca416>3.0.co;2-k
• 作为产物：
  描述：

  (5R)-5-isopropyl-2-methylene cyclohexanol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以100%的产率得到(5R)-2-methylidene-5-isopropylcyclohexanone
  参考文献：
  名称：

  Synthesis of (−)-Erythrodiene and (+)-7-Epispirojatamolvia Intramolecular Pd-Catalyzed Allylzincation

  摘要：

  Two spirobicyclic sesquiterpenoids, (-)-erythrodiene (1) and (+)-7-epispirojatamol (30),were synthesized in enantiomerically pure form via an intramolecular allylzincation process. The allylzinc species were formed in the presence of Et,Zn via transmetallation of a catalytically generated allylpalladium intermediate. Several Pd catalysts were tested for this transformation, and [Pd(OAc)(2)/Bu3P(1 equiv.) was found to be, by far, the most effective. Whereas the preparation of 1 involved allylzincation of a tethered terminal olefin. 30 was formed via a novel intramolecular allylzincation of a methyl ketone. Both reactions showed the same stereochemical preference. yielding the spirobicyclic products in 95:5 and 4:1 diastereoisomer ratios, respectively.

  DOI：

  10.1002/1522-2675(20010228)84:2<416::aid-hlca416>3.0.co;2-k

文献信息

• Synthesis of the Alleged Natural Monoterpenoid ?-Santolinenone
  作者：Graizano Guella、Marino Cavazza、Antonio Guerriero、Francesco Pietra

  DOI：10.1002/hlca.19840670511

  日期：1984.8.8

  Authentic α-santolinenone ( = (+)-(4R)-1(7)-p-menthen-2-one; (+)-1) is made available for the the first time in 30% overall yield from (+)-(4R)-p-menthene ((+)-2) via the diastereoisomeric allylic alcohols (+)-4a/(+)-4b, which are oxidized to (+)-1 with Ag2CO3/Celite. Yields are good, except for the last stage; indeed, only alcohol (+)-4a, with equatorial OH-group, undergoes oxidation, and (+)-1 is

  首次以（+）的30％的总收率首次获得纯正的α-山梨烯酮（=（+）-（4 R）-1（7）-p-薄荷2-一;（+）- 1） ）-（4 R）-对-薄荷烯（（+）- 2）通过非对映异构的烯丙醇（+）- 4a /（+）- 4b被Ag 2 CO 3 /硅藻土氧化为（+）- 1。除最后阶段外，收率良好。的确，只有醇（+） - 4a中，与赤道OH基团，经受氧化，和（+） - 1被部分地中减去通过杂Diels-Alder二聚，得到非对映异构体二氢吡喃（+）- 5a /（+）- 5b的混合物。当使用Cr（VI）试剂ae时，（+）- 4a /（+）- 4b主要产生蛇（草（6）和甲氧丙酮（7），NnO 2与（+）- 4a /（+）- 4b反应太慢。以前认为是1的樟脑热解产物必须是另一种化合物，可能是7。
• Synthesis of (−)-Erythrodiene and (+)-7-Epispirojatamolvia Intramolecular Pd-Catalyzed Allylzincation
  作者：Wolfgang Oppolzer、Felix Flachsmann

  DOI：10.1002/1522-2675(20010228)84:2<416::aid-hlca416>3.0.co;2-k

  日期：2001.2.28

  Two spirobicyclic sesquiterpenoids, (-)-erythrodiene (1) and (+)-7-epispirojatamol (30),were synthesized in enantiomerically pure form via an intramolecular allylzincation process. The allylzinc species were formed in the presence of Et,Zn via transmetallation of a catalytically generated allylpalladium intermediate. Several Pd catalysts were tested for this transformation, and [Pd(OAc)(2)/Bu3P(1 equiv.) was found to be, by far, the most effective. Whereas the preparation of 1 involved allylzincation of a tethered terminal olefin. 30 was formed via a novel intramolecular allylzincation of a methyl ketone. Both reactions showed the same stereochemical preference. yielding the spirobicyclic products in 95:5 and 4:1 diastereoisomer ratios, respectively.