(6E,14E,18E)-2,6,10,15,19,23-hexamethyl-tetracosa-2,6,14,18,22-pentaene-10,11-diol | 144641-00-9

• 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: (6E,14E,18E)-2,6,10,15,19,23-hexamethyl-tetracosa-2,6,14,18,22-pentaene-10,11-diol
• 英文别名: squalene 10,11-glycol；(6E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,14,18,22-pentaene-10,11-diol
• CAS: 144641-00-9
• 化学式: C₃₀H₅₂O₂
• 分子量: 444.742
• InChiKey: DKVIPPGREJURCX-JSFDVHLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  32
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (6E,14E,18E)-2,6,10,15,19,23-hexamethyl-tetracosa-2,6,14,18,22-pentaene-10,11-diol 在 4-二甲氨基吡啶 、 potassium peroxymonosulfate 、 Shi's ketone 、 2K⁽¹⁺⁾*CO₃^(2-)*0.5H₂O=K₂CO₃*0.5H₂O 、 四丁基硫酸氢铵 、 disodium ethylenediaminetetraacetic acid 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 10.5h， 生成
  参考文献：
  名称：

  （-）-Glabrescol的两个简洁的对映选择性全合成暗示从角鲨烯开始的替代生物合成途径

  摘要：

  所述Ç 2 -对称（ - ） - glabrescol在从两个步骤（10合成小号，11 - [R ）-二羟基-10,11- dihydrosqualene或角鲨烯与分别为50％或10％的总产率，。这些高效且仿生的合成过程采用了碱促进的中端至双端双环氧化物开放级联反应，该反应可在一次操作中在甘草糖醇中构建五个四氢呋喃环。

  DOI：

  10.1021/ol3016836
• 作为产物：
  描述：

  角鲨烯 在 间氯过氧苯甲酸 、 高氯酸 作用下， 以 二氯甲烷 、 四氢呋喃 、 水 为溶剂， 反应 4.0h， 以12%的产率得到(10E,14E,18E)-2,6,10,15,19,23-hexamethyl-tetracosa-2,10,14,18,22-pentaene-6,7-diol
  参考文献：
  名称：

  （-）-Glabrescol的两个简洁的对映选择性全合成暗示从角鲨烯开始的替代生物合成途径

  摘要：

  所述Ç 2 -对称（ - ） - glabrescol在从两个步骤（10合成小号，11 - [R ）-二羟基-10,11- dihydrosqualene或角鲨烯与分别为50％或10％的总产率，。这些高效且仿生的合成过程采用了碱促进的中端至双端双环氧化物开放级联反应，该反应可在一次操作中在甘草糖醇中构建五个四氢呋喃环。

  DOI：

  10.1021/ol3016836

文献信息

• Enzymatic cyclizations of squalene analogs with threo- and erythro-diols at the 6,7- or 10,11-positions by recombinant squalene cyclase. Trapping of carbocation intermediates and mechanistic insights into the product and substrate specificities
  作者：Takamasa Abe、Tsutomu Hoshino

  DOI：10.1039/b506590a

  日期：——

  [2,1-b]oxepine and malabaricane skeletons, almost of which are novel compounds. These products indicate that 6-membered monocyclic, 6/6-fused bicyclic and 6/6/5-fused tricyclic cations were involved in the cyclization reaction in addition to acyclic cation. All the trapped cations were the stable tertiary cation, but not the secondary one, indicating that the polycyclization reaction proceeds with

  为了捕获在角鲨烯环化级联过程中形成的碳正离子中间体，将在6,7-和10,11-位的具有邻-和赤-二醇的角鲨烯类似物与来自酸热脂环酸杆菌的重组角鲨烯环化酶一起进行温育，从而进行了构建的三萜与四氢吡喃，八氢萘，具有羰基的十氢萘，十二氢苯并[f]色烯，十四氢萘[2,1-b]氧杂环丁烷和马拉巴烷烷骨架，几乎都是新化合物。这些产物表明除无环阳离子外，环化反应还涉及6元单环，6 / 6-稠合的双环和6/6 / 5-稠合的三环阳离子。所有被捕获的阳离子都是稳定的叔阳离子，但不是次要的，表明多环化反应是通过马尔可夫尼科夫封闭进行的。产物概况表明，除了对映选择性之外，环化反应还伴随产物和底物特异性而进行。对观察到的立体化学特异性的机械观察表明，角鲨烯二醇的预先组织的椅子构象受到环化酶的严格限制，并且在反应腔中不允许自由运动或构象变化，因此，底物和产物的特异性是主要由亲核羟基向中间碳正离子的最少运动定向；羟基
• Internal Oxidosqualenes: Determination of Absolute Configuration and Activity as Inhibitors of Purified Pig Liver Squalene Epoxidase
  作者：Jose-Luis Abad、Josefina Casas、Francisco Sanchez-Baeza、Angel Messeguer

  DOI：10.1021/jo00117a014

  日期：1995.6

  The preparation and characterization of oxidosqualenes 3-(6R,7R), 3-(6S,7S), 4-(10R,11R), and 4-(10S,11S) is reported. Squalenediol 6 was converted into the corresponding mixture of(R)-Mosher esters 8 and 9, which were separated by semipreparative HPLC. Esters 8 and 9 were reduced to the chiral diols 6-(6R,7S) and 6-(6S,7R), respectively, which were finally converted into the corresponding epoxides 3-(6R,7R) and 3-(6S,7S). A similar procedure was used for the preparation of chiral epoxy derivatives 4-(10R,11R) and 4-(10S,11S) from esters 10 and 11, respectively. The determination of the absolute configuration of these epoxides was carried out by using the method reported by Ohtani et al. (J. Am. Chem. Sec. 1991, 113, 4092), which was adapted to the case of racemic mixtures from synthetic origin. For this purpose, the (R)-Mosher esters derived from the enantiomers of squalenediols 6 or 7 were used. The validity of this approach was confirmed by the absolute configuration found for the three squalenediols 6-(6R,7R), 6-(6S,7S), 7-(10R,11R), and 7-(10S,11S) formed in the Sharpless asymmetric dihydroxylation of squalene (Crispino, G. A.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 4273). Results on the inhibitory activity of oxidosqualenes 3-(6R,7R), 3-(6S,7S), 4-(10R,11R), and 4-(10S,11S) using purified squalene epoxidase (SE) fi om pig liver showed that epoxide 3-(6S,7S) was the best inhibitor within the compounds assayed (IC50 = 6.7 mu M), although oxidosqualene 4-(10R,11R) also exhibited a moderate inhibitory activity (IC50 = 25 mu M). The inhibition elicited by the epoxy derivative 3-(6S,7S) was competitive with respect to squalene (K-i = 2.7 mu M). This activity is comparable to that reported for the most potent competitive SE inhibitors described so far. Finally, incubation of oxidosqualene 3-(6S,7S) with purified SE led to the formation of dioxidosqualene 22-(3S,6S,7S), whereas its regioisomer 23-(3S,18S,19S) was not detected. In contrast, incubation of epoxide 3-(6R,7R) under the same conditions afforded a mixture of dioxides 22-(3S,6R,7R) and 23-(3S,18R,19R) in a 5:12 molar ratio. The fact that oxidosqualenes 3 and 4 have been found in nature, and our previous results showing that racemic dioxide 23 is a potent inhibitor of oxidosqualene-lanosterol cyclase in rat liver microsomes (Abad, J. L.; et al. J. Org. Chem. 1993, 58, 3991), confers a potential physiological relevance to the results reported herein.
• Two Concise Enantioselective Total Syntheses of (−)-Glabrescol Implicate Alternative Biosynthetic Pathways Starting from Squalene
  作者：Peng Yang、Pei-Fang Li、Jin Qu、Liang-Fu Tang

  DOI：10.1021/ol3016836

  日期：2012.8.3

  The C2-symmetric (−)-glabrescol was synthesized in two steps from (10S,11R)-dihydroxy-10,11-dihydrosqualene or squalene with 50% or 10% overall yields, respectively. These highly efficient and biomimetic syntheses employed a base-promoted middle-to-terminal double epoxide-opening cascade, which constructs the five tetrahydrofuran rings in glabrescol in one operation.

  所述Ç 2 -对称（ - ） - glabrescol在从两个步骤（10合成小号，11 - [R ）-二羟基-10,11- dihydrosqualene或角鲨烯与分别为50％或10％的总产率，。这些高效且仿生的合成过程采用了碱促进的中端至双端双环氧化物开放级联反应，该反应可在一次操作中在甘草糖醇中构建五个四氢呋喃环。