epsilon-carotene | 38894-81-4

• 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: epsilon-carotene
• 英文别名: ε,ε-carotene；ε-carotene；all-trans-ε-carotene；all-trans-ε-Carotin；ε,ε-Carotin；β-Carotin；1,5,5-trimethyl-6-[(1E,3E,5E,7E,9E,11E,13E,15E,17E)-3,7,12,16-tetramethyl-18-(2,6,6-trimethylcyclohex-2-en-1-yl)octadeca-1,3,5,7,9,11,13,15,17-nonaenyl]cyclohexene
• CAS: 38894-81-4
• 化学式: C₄₀H₅₆
• 分子量: 536.885
• InChiKey: QABFXOMOOYWZLZ-JLTXGRSLSA-N

物化性质

• 熔点：
  190 °C
• 沸点：
  635.2±55.0 °C(Predicted)
• 密度：
  0.935±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13.7
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  epsilon-carotene 在 sodium tetrahydroborate 、 水 、 三氟乙酸 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 0.17h， 生成 斑蝥黄
  参考文献：
  名称：

  电荷离位的类胡萝卜素单和药的亲核反应。

  摘要：

  在本研究中，通过与BF3-醚酸酯进行反应而制得的二芳基（phi，phi-胡萝卜素，异戊二烯）和脂肪族（psi，psi-胡萝卜素，番茄红素）胡萝卜素的阳离子混合物，与β相比，具有更大的复杂性，从而获得了见识。 β-胡萝卜素。由烯丙基类胡萝卜素β，β-胡萝卜素-4-醇（异隐黄质）和β，β-胡萝卜素-4,4'-二醇（异玉米黄质），以及异戊二烯和番茄红素原位制备的单药和除草剂的化学反应是使用选定的O，N和S亲核试剂进行调查; 水，甲醇，叠氮化物和硫代乙酸盐。共分离出22种产品，包括18种新的中性类胡萝卜素产品，并通过VIS，MS和NMR（部分）光谱进行鉴定。它们的结构与阳离子中间体的结构相容。在各种药物中正式添加氢化物，合理化次要反应产物所必需的化合物，将在阳离子反应中更可能发生氢自由基或质子转移的方面进行讨论。对于所有淬灭产物，观察到广泛的E / Z异构化。讨论了类胡萝卜素阳离子在合成4 ,,（

  DOI：

  10.1039/b406913g
• 作为产物：
  描述：

  斑蝥黄 在 sodium tetrahydroborate 、 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 生成 epsilon-carotene
  参考文献：
  名称：

  电荷离位的类胡萝卜素单和药的亲核反应。

  摘要：

  在本研究中，通过与BF3-醚酸酯进行反应而制得的二芳基（phi，phi-胡萝卜素，异戊二烯）和脂肪族（psi，psi-胡萝卜素，番茄红素）胡萝卜素的阳离子混合物，与β相比，具有更大的复杂性，从而获得了见识。 β-胡萝卜素。由烯丙基类胡萝卜素β，β-胡萝卜素-4-醇（异隐黄质）和β，β-胡萝卜素-4,4'-二醇（异玉米黄质），以及异戊二烯和番茄红素原位制备的单药和除草剂的化学反应是使用选定的O，N和S亲核试剂进行调查; 水，甲醇，叠氮化物和硫代乙酸盐。共分离出22种产品，包括18种新的中性类胡萝卜素产品，并通过VIS，MS和NMR（部分）光谱进行鉴定。它们的结构与阳离子中间体的结构相容。在各种药物中正式添加氢化物，合理化次要反应产物所必需的化合物，将在阳离子反应中更可能发生氢自由基或质子转移的方面进行讨论。对于所有淬灭产物，观察到广泛的E / Z异构化。讨论了类胡萝卜素阳离子在合成4 ,,（

  DOI：

  10.1039/b406913g

文献信息

• Practical Synthesis of ε-Carotene
  作者：Runpu Shen、Chunlei Wu、Ruiwei Cao、Xiaohua Song、Chunlei Lv、Weidong Ye、Shiqing Pi、Chaohui Chen

  DOI：10.1055/s-0034-1378941

  日期：——

  give ε-carotene. The synthetic steps are easily performed and are practical for large-scale production. A novel route for the total synthesis of ε-carotene is described. The synthesis is based on a condensation between α-cyclocitral and diethyl [(2E)-3-methoxy-2-methylprop-2-en-1-yl]phosphonate to give a C14 enol ether, hydrolysis of the C14-enol ether to a give a C14 aldehyde, and a modified Wittig–Horner

  摘要 描述了一种全合成ε-胡萝卜素的新颖途径。合成是基于之间的缩合α-环柠檬醛和二[（2- ë）-3-甲氧基-2-甲基丙-2-烯-1-基]膦酸酯以得到一个C 14烯醇醚，将C的水解14 -烯醇醚到一个给一个C 14醛和C的变形Wittig-Horner反应15从C膦酸酯14醛和C 10三烯二醛，得到ε胡萝卜素。合成步骤容易进行并且对于大规模生产是实用的。 描述了一种全合成ε-胡萝卜素的新颖途径。合成是基于之间的缩合α-环柠檬醛和二[（2- ë）-3-甲氧基-2-甲基丙-2-烯-1-基]膦酸酯以得到一个C 14烯醇醚，将C的水解14 -烯醇醚到一个给一个C 14醛和C的变形Wittig-Horner反应15从C膦酸酯14醛和C 10三烯二醛，得到ε胡萝卜素。合成步骤容易进行并且对于大规模生产是实用的。
• One ring or two? Determination of ring number in carotenoids by lycopene ɛ-cyclases
  作者：Francis X. Cunningham、Elisabeth Gantt

  DOI：10.1073/pnas.051618398

  日期：2001.2.27

  Carotenoids in the photosynthetic membranes of plants typically contain two β-rings (e.g., β-carotene and zeaxanthin) or one ɛ- and one β-ring (e.g., lutein). Carotenoids with two ɛ-rings are uncommon. We reported earlier that the Arabidopsis thaliana lycopene ɛ-cyclase (LCYe) adds one ɛ-ring to the symmetrical linear substrate lycopene, whereas the structurally related lycopene β-cyclase (LCYb) adds two β-rings. Here we describe a cDNA encoding LCYe in romaine lettuce ( Lactuca sativa var. romaine), one of the few plant species known to accumulate substantial quantities of a carotenoid with two ɛ-rings: lactucaxanthin. The product of the lettuce cDNA, similar in sequence to the Arabidopsis LCYe (77% amino acid identity), efficiently converted lycopene into the bicyclic ɛ-carotene in a heterologous Escherichia coli system. Regions of the lettuce and Arabidopsis ɛ-cyclases involved in the determination of ring number were mapped by analysis of chimeric ɛ-cyclases constructed by using an inverse PCR approach. A single amino acid was found to act as a molecular switch: lettuce LCYe mutant H457L added only one ɛ-ring to lycopene, whereas the complementary Arabidopsis LCYe mutant, L448H, added two ɛ-rings. An R residue in this position also yields a bi-ɛ-cyclase for both the lettuce and Arabidopsis enzymes. Construction and analysis of chimera of related enzymes with differing catalytic activities provide an informative approach that may be of particular utility for studying membrane-associated enzymes that cannot easily be crystallized or modeled to existing crystal structures.

  植物光合膜中的类胡萝卜素通常包含两个β-环（例如β-胡萝卜素和玉米黄质）或一个ɛ-环和一个β-环（例如叶黄素）。具有两个ɛ-环的类胡萝卜素很少见。我们之前报道过拟南芥番茄红素ɛ-环化酶（LCYe）将对称线性底物番茄红素加入一个ɛ-环，而结构相关的番茄红素β-环化酶（LCYb）则加入两个β-环。在这里，我们描述了罗曼生菜（Lactuca sativa var. romaine）中编码LCYe的cDNA，罗曼生菜是为数不多的已知积累大量具有两个ɛ-环的类胡萝卜素（lactucaxanthin）的植物物种之一。与拟南芥LCYe相似的产物（77％氨基酸同源性）有效地将番茄红素转化为双环ɛ-胡萝卜素，在异源大肠杆菌系统中。通过使用反向PCR方法构建的嵌合ɛ-环化酶的分析，映射了罗曼生菜和拟南芥ɛ-环化酶中决定环数的区域。发现单个氨基酸作为分子开关：罗曼生菜LCYe突变体H457L仅向番茄红素添加一个ɛ-环，而互补的拟南芥LCYe突变体L448H添加两个ɛ-环。该位置的R残基也为罗曼生菜和拟南芥酶产生双ɛ-环化酶。构建和分析具有不同催化活性的相关酶的嵌合体，提供了一种有益的方法，特别适用于研究不能轻易结晶或建模到现有晶体结构的膜相关酶。
• Palladium‐Catalyzed <i>S</i>‐Allylation of Vinyl Carbinols – Total Syntheses of Carotenoids by Julia‐Kocienski Olefination
  作者：Aleksei N. Golikov、Chibeom Seo、Jae Hwan Lee、Sangho Koo

  DOI：10.1002/adsc.202301055

  日期：2024.1.9

  Palladium catalyzed S-allylation of vinyl carbinols from ionones (or conjugated carbonyls) with 2-mercapto-1,3-benzothiazole (BT-SH) provides versatile C15 dienyl benzothiazolyl (BT) sulfides. This Pd(dppe)Cl2-catalyzed S-allylation is highly selective for free allylic alcohols in the presence of allylic acetates, resulting in 3- or 4-acetoxy C15 dienyl BT-sulfides suitable for xanthophyll synthesis

  钯催化紫罗兰酮（或共轭羰基）与 2-巯基-1,3-苯并噻唑 (BT-SH) 发生乙烯基甲醇的 S-烯丙基化反应，得到多用途的 C 15二烯基苯并噻唑基 (BT) 硫化物。这种Pd(dppe)Cl 2催化的S-烯丙基化在烯丙乙酸酯存在下对游离烯丙醇具有高度选择性，产生适合叶黄素合成的3-或4-乙酰氧基C 15二烯基BT-硫化物。相应的C 15二烯基BT-砜与C 10 2,7-二甲基-2,4,6-辛三烯二醛在温和条件下进行Julia-Kocienski烯化反应，生成类胡萝卜素天然产物。实现了一系列类胡萝卜素的高效合成，包括叶黄素（如异玉米黄质、玉米黄质和叶黄素）以及胡萝卜素（如 β-胡萝卜素、ε-胡萝卜素和 9'- Z-苯基胡萝卜素）。
• A Unique Polyene Pigment of the Marine Diatom Navicula Torquatum
  作者：Harold H. Strain、Winston M. Manning

  DOI：10.1021/ja01251a507

  日期：1943.11
• A novel type of lycopene ε-cyclase in the marine cyanobacterium Prochlorococcus marinus MED4
  作者：Per Stickforth、Sabine Steiger、Wolfgang R. Hess、Gerhard Sandmann

  DOI：10.1007/s00203-003-0545-4

  日期：2003.6

  Chlorophyll-b-possessing cyanobacteria of the genus Prochlorococcus share the presence of high amounts of alpha- and beta-carotenoids with green algae and higher plants. The branch point in carotenoid biosynthesis is the cyclization of lycopene, for which in higher plants two distinct enzymes are required, epsilon- and beta-lycopene cyclase. All cyanobacteria studied so far possess a single beta-cyclase. Here, two different Prochlorococcus sp. MED4 genes were functionally identified by heterologous gene complementation in Escherichia coli to encode lycopene cyclases. Whereas one is both functionally and in sequence highly similar to the beta-cyclase of Synechococcus sp. strain PCC 7942 and other cyanobacteria, the other showed several intriguing features. It acts as a bifunctional enzyme catalyzing the formation of epsilon- as well as of beta-ionone end groups. Expression of this cyclase in E. coli resulted in the simultaneous accumulation of alpha- beta-, delta-, and epsilon-carotene. Such an activity is in contrast to all lycopene epsilon-cyclases known so far, including those of the higher plants. Thus, for the first time among prokaryotes, two individual enzymes were identified in one organism that are responsible for the formation of cyclic carotenoids with either beta- or epsilon-end groups. These two genes are suggested to be designated as crtL-b and crtL-e. The results indicate that both enzymes might have originated from duplication of a single gene. Consequently, we suggest that multiple gene duplications followed by functional diversification resulted several times, and in independent lineages, in the appearance of enzymes for the biosynthesis of cyclic carotenoids.