(3R)-(6E,10E,14E,18E)-2,3-dihydroxy-2,3-dihydrosqualene | 63976-65-8

• 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: (3R)-(6E,10E,14E,18E)-2,3-dihydroxy-2,3-dihydrosqualene
• 英文别名: (3R)-2,3-dihydroxy-2,3-dihydrosqualene；(R)-2,3-dihydroxy-2,3-dihydrosqualene；2,3(R)-Dihydroxy-2,3-dihydrosqualene；2,3-(R)-dihydroxysqualene；(3R,all-E)-2,6,10,15,19,23-hexamethyl-tetracosa-6,10,14,18,22-pentaene-2,3-diol；(+)-squalene 2,3-glycol；(3R,6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-6,10,14,18,22-pentaene-2,3-diol
• CAS: 63976-65-8
• 化学式: C₃₀H₅₂O₂
• 分子量: 444.742
• InChiKey: GRPNWQFOKYUABH-DLBGYGIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 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：

  (3R)-(6E,10E,14E,18E)-2,3-dihydroxy-2,3-dihydrosqualene 在 Oxone 、 Shi's ketone Sodium tetraborate decahydrate 、 四丁基硫酸氢铵 、 edetate disodium 作用下， 以 水 、 乙腈 为溶剂， 反应 1.5h， 生成 (3R)-5-[(2R,3R)-3-[2-[(2R,3R)-3-[2-[(2R,3R)-3-[2-[(2R,3R)-3-[2-[(2R)-3,3-dimethyloxiran-2-yl]ethyl]-3-methyloxiran-2-yl]ethyl]-3-methyloxiran-2-yl]ethyl]-2-methyloxiran-2-yl]ethyl]-2-methyloxiran-2-yl]-2-methylpentane-2,3-diol
  参考文献：
  名称：

  归因于角鲨烯类 Glabrescol 和三种 Cs 对称非对映异构体的五环 Cs 对称结构的简单全合成迫使结构修正

  摘要：

  DOI：

  10.1021/ja000842y
• 作为产物：
  描述：

  角鲨烯 在 四氧化锇 、 甲基磺酰胺 、 potassium carbonate 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 potassium hexacyanoferrate(III) 作用下， 以 叔丁醇 为溶剂， 反应 48.0h， 以12%的产率得到(3R)-(6E,10E,14E,18E)-2,3-dihydroxy-2,3-dihydrosqualene
  参考文献：
  名称：

  沸石NaY促进的环氧多烯萜烯单环化：直接合成不完全环化的天然萜烯的独特途径

  摘要：

  通过限制在NaY沸石中，各种环氧多烯萜容易环化，主要形成单环化产物。不管环氧萜烯的侧链如何，单环化途径都非常占优势，而单环产物具有区域选择性地具有外亚甲基双键。在乙酸法呢烯基乙酸酯，环氧法呢烯基丙酮或2,3-环氧角鲨烯的情况下，选择性单环化为合成多种天然产物（例如榄香二醇，法呢香酚B–D，阿奇儿醇A，山茶酚C和四种法呢基丙酮）提供了直接途径。褐藻中提取的代谢产物。由（S的环化引起的Achilleol A的旋光。基）-2,3-环氧角鲨烯与天然产物的匹配，从而achilleol A的绝对构型确定为1小号，3 - [R 。从机理的角度来看，NaY促进的9,10-环氧香叶基丙酮（在氘代C-10甲基上进行选择性氘标记）的环化相对于宝石-二甲基基团的局部立体选择性> 97％。这一结果与协调机制相吻合。最后，我们首次通过标记实验证明，环氧多烯萜烯在酸催化下向2,3,4-三甲基环己酮的仿生转化是高度立体选

  DOI：

  10.1002/adsc.200800180

文献信息

• Production of epoxydammaranes by the enzymatic reactions of (3R)- and (3S)-2,3-squalene diols and those of 2,3:22,23-dioxidosqualenes with recombinant squalene cyclase and the mechanistic insight into the polycyclization reactions
  作者：Tsutomu Hoshino、Yukie Yonemura、Takamasa Abe、Yumi Sugino

  DOI：10.1039/b615897h

  日期：——

  The enzymatic cyclizations of (3R)- and (3S)-2,3-squalene diols by squalene cyclase afforded bicyclic compounds and epoxydamamranes in a ca. 3 : 2 ratio. Formation of the epoxydammarane scaffold indicates that a 6/6/6/5-fused tetracyclic cation is involved as the intermediate in the polycyclization reaction. 2,3:22,23-Dioxidosqualenes also afforded an epoxydammarane skeleton, i.e., 3α- or 3β-hydroxyepoxydammaranes, but the amount of bicyclic compounds produced was markedly lower than that of the squalene diols, indicating that the larger steric bulk of the diols had a more significant influence on the polycyclization pathway than the smaller bulk of the expoxide. All the epoxydammaranes had 17R,20R stereochemistry except for one product, demonstrating that these analogs were folded into an all-chair conformation in the reaction cavity. The mechanistic insight into the observed stereochemical specificities indicated that the organized all-chair conformation is rigidly constricted by squalene cyclase and, thus, free conformational change is not allowed inside the reaction cavity; a small rotation of the hydroxyl group or the epoxide toward the intermediary cation gave a high yield of the enzymatic products, while a large rotation led to a low yield of the product. The stereochemistries of the generated epoxydammaranes are opposite to those from natural sources, and thus almost all of the enzymatic products described here are novel.

  通过角鲨烯环化酶对(3R)-和(3S)-2,3-鲨烯二醇进行酶环化，可得到双环化合物和环氧达玛烷，两者的比例约为 3:2。环氧达玛烷支架的形成表明，6/6/6/5-融合的四环阳离子作为中间体参与了多环化反应。2,3:22,23-二氧二十二烷也能产生环氧达玛烷骨架，即 3α- 或 3β- 羟基环氧达玛烷，但产生的双环化合物的数量明显低于角鲨烯二醇，这表明二醇较大的立体体积对多环化途径的影响要大于较小的过氧化物体积。除一种产物外，所有环氧达玛烷都具有 17R、20R 立体化学结构，这表明这些类似物在反应腔中折叠成全椅构象。对所观察到的立体化学特异性的机理认识表明，有组织的全椅构象受到角鲨烯环化酶的严格限制，因此反应腔内不允许自由构象变化；羟基或环氧化物朝中间阳离子方向的微小旋转可产生高产率的酶促产物，而较大的旋转则导致产物的低产率。生成的环氧达玛烷的立体化学结构与天然来源的环氧达玛烷相反，因此这里描述的几乎所有酶产物都是新的。
• Asymmetric dihydroxylation of squalene
  作者：Gerard A. Crispino、K.Barry Sharpless

  DOI：10.1016/s0040-4039(00)74236-5

  日期：1992.7

  The asymmetric dihydroxylation of squalene was studied using the new ligand (DHQD)2-PHAL. Moderate positional selectivity for the 2,3-olefin was observed with high % ee.

  使用新的配体（DHQD）2 -PHAL研究了角鲨烯的不对称二羟基化。在高ee百分比下，观察到对2,3-烯烃的中等位置选择性。
• Arylacetic acid derivatization of 2,3- and internal erythro-squalene diols. Separation and absolute configuration determination
  作者：José-Luis Abad、Francisco Camps

  DOI：10.1016/j.tet.2004.09.059

  日期：2004.12

  We have studied a new approach for the resolution and absolute configuration determination of the enantiomers of squalene diols as intermediate precursors in the chemical synthesis of different squalene oxides (SOs); (3R)- and (3S)-2,3-SO, (6R,7R)- and (6S,7S)-6,7-SO, and (10R,11R)- and (10S,11S)-10,11-SO. Monoderivatization of the corresponding racemic squalene diol intermediates with pure stereoisomers

  我们研究了一种新的方法，用于拆分和制备角鲨烯二醇的对映异构体，作为对映异构体的绝对构型，该对映体是化学合成不同的角鲨烯氧化物（SOs）的中间前体。（3 R）-和（3 S）-2,3-SO，（6 R，7 R）-和（6 S，7 S）-6,7-SO和（10 R，11 R）-和（10 S，11 S）-10,11-SO。相应的外消旋角鲨烯二醇中间体与（S）-（+）-甲氧基苯基乙酸（（S）-（+）-MPA），（S）-（+）-9-甲氧基甲氧基乙酸（（S）-（+）-9-AMA）和（S）-（+）-乙酰氧基苯基乙酸（（S）-（+）-APA）提供了非对映体酯，其可以通过硅胶快速柱色谱法容易地分离。另外，有利的是根据描述的这些衍生手性试剂的模型，由1 H NMR数据推断出这些衍生的二醇的这些非对映异构体的绝对构型。为了证明不同的立体异构体的绝对构型的分配，（小号） - （+） - AMA显示较大的Δ δ由1 H NMR，然而，（小号）
• A mechanistically designed bis-cinchona alkaloid ligand allows position- and enantioselective dihydroxylation of farnesol and other oligoprenyl derivatives at the terminal isopropylidene unit
  作者：E.J. Corey、Mark C. Noe、Shouzhong Lin

  DOI：10.1016/0040-4039(95)01920-d

  日期：1995.11

  The mechanistically designed bis-cinchona alkaloid derivative 3 serves as an excellent catalytic ligand in the OsO4-promoted catalytic enantioselective dihydroxylation of the terminal isopropylidene group in farnesyl, geranylgeranyl, and solanesyl esters and also squalene, with selectivity as high as 120:1 with E,E-farnesyl acetate. H-1 NMR and X-ray studies support the conformation described by 3 in which the U-shaped catalytic binding pocket is composed of the two 6-(4-heptyloxy)-quinoline units (sides and rear) and the naphthopyridazine linker (bottom).
• Highly Effective Transition Structure Designed Catalyst for the Enantio<i>- </i>and Position<i>-</i>Selective Dihydroxylation of Polyisoprenoids
  作者：E. J. Corey、Junhu Zhang

  DOI：10.1021/ol016577i

  日期：2001.10.1

  GRAPHICSThe chiral monocinchona derivative shown, synthesized in one step from two efficiently prepared chiral building blocks, was designed under mechanistic guidance as a catalyst for the enantio- and position-selective dihydroxylation of the terminal isopropylidene group of polylsoprenoids. Its efficacy as a synthetic reagent for this purpose was demonstrated for several different substrates.