(-)-(2S,5S)-ethyl <(3-isopropyl-1-methyl-2-methylene)-cyclopentane>-1-acetate | 134107-43-0

• 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: (-)-(2S,5S)-ethyl <(3-isopropyl-1-methyl-2-methylene)-cyclopentane>-1-acetate
• 英文别名: (-)-(2S,5S)-5-isopropyl-2-methyl-2-(carboethoxymethyl)methylenecyclopentane；ethyl 3-isopropyl-2-methylene-1-methylcyclopentaneacetate；ethyl 2-[(1S,3S)-1-methyl-2-methylidene-3-propan-2-ylcyclopentyl]acetate
• CAS: 134107-43-0
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: ODEJRLGJMBCDET-JSGCOSHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(2S,5S)-ethyl <(3-isopropyl-1-methyl-2-methylene)-cyclopentane>-1-acetate 在 吡啶 、 sodium hydroxide 、 草酰氯 、 三氟化硼乙醚 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 40.33h， 生成 (3aR,6aS)-2-[3-(tert-Butyl-dimethyl-silanyloxy)-2,2-dimethyl-propyl]-4-isopropylidene-3a,6a-dimethyl-octahydro-pentalen-2-ol
  参考文献：
  名称：

  来自（R）-（+）-柠檬烯的聚醌。对映体全合成新型三环倍半萜烯（-）-ceratopicanol

  摘要：

  已经完成了对生物遗传学上重要且结构新颖的三喹烷倍半萜烯（-）-ceretatopicanol的首次全合成。

  DOI：

  10.1039/c39910001367
• 作为产物：
  描述：

  (5S)-isopropyl-2-methylcyclopent-1-enecarboxaldehyde 在 sodium tetrahydroborate 、 cerium(III) chloride 、 mercury(II) diacetate 、 丙酸 作用下， 以 甲醇 为溶剂， 反应 13.5h， 生成 (-)-(2S,5S)-ethyl <(3-isopropyl-1-methyl-2-methylene)-cyclopentane>-1-acetate
  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

• Application of microwave heating technique for rapid synthesis of γ,δ-unsaturated esters
  作者：Adusumilli Srikrishna、Sankuratri Nagaraju、Paturu Kondaiah

  DOI：10.1016/0040-4020(94)01058-8

  日期：1995.2

  The use of microwave heating technique for the acceleration of ortho ester Claisen rearrangement (a three step transformation) is described. Irradiation of a DMF solution of the allyl alcohol , triethyl orthoacetate and propionic acid (catalytic) in an Erlenmeyer flask for 10 minutes in a microwave oven generated the ester in 83% yield. Analogously, ortho ester Claisen rearrangement of a variety of

  描述了使用微波加热技术加速原酸酯克莱森重排（三步转化）。将烯丙醇，原乙酸三乙酯和丙酸的DMF溶液在微波炉中在锥形烧瓶中辐射10分钟（生成酯），产率为83％。类似地，原酸酯克莱森多种烯丙基和炔丙基醇的重排（，）得以实现。在15分钟内通过两个烯丙醇部分的原酸酯Claisen重排（涉及六个步骤）由2-丁炔-1,4-二醇（）形成二酯，证明了微波加热技术的多功能性。
• An Enantiospecific Approach to the 5-8-5 Tricyclic System of Basmanes
  作者：A. Srikrishna、Gopalasetty Nagaraju、G. Ravi

  DOI：10.1055/s-0030-1259073

  日期：2010.12

  An enantiospecific synthesis of the 5-8-5 tricyclic ring system present in the basmane diterpenes has been accomplished, starting from ethyl 3-isopropyl-2-methylene-1-methylcyclopentane­acetate [readily available in five steps from (R)-limonene] employing an RCM reaction for the annulation of cyclooctane and an intramolecular rhodium carbenoid CH insertion reaction for the construction of the cyclopentane ring.

  从乙基3-异丙基-2-亚甲基-1-甲基环戊烷乙酸酯（可从右旋柠檬烯通过五个步骤轻松获得）开始，采用RCM反应环合环辛烷，并利用分子内铑羰基CH插入反应构建环戊烷环，完成了巴斯曼二萜中5-8-5三环环系统的对映选择性合成。
• Srikrishna; Nagaraju, Gopalasetty, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2011, vol. 50, # 1, p. 73 - 76
  作者：Srikrishna、Nagaraju, Gopalasetty

  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：——
• Srikrishna Adusumilli, Nagaraju Sankuratri, Kondaiah Paturu, Tetrahedron, 51 (1995) N 6, S 1809-1816
  作者：Srikrishna Adusumilli, Nagaraju Sankuratri, Kondaiah Paturu

  DOI：——

  日期：——