hopane-3β,22-diol | 22149-65-1

• 物质功能分类: 天然产物 - 萜类
• 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: hopane-3β,22-diol
• 英文别名: 3β-hydroxyhopanol；Hopane-3beta,22-diol；(3S,3aS,5aR,5bR,7aR,9S,11aR,11bR,13aR,13bS)-3-(2-hydroxypropan-2-yl)-5a,5b,8,8,11a,13b-hexamethyl-1,2,3,3a,4,5,6,7,7a,9,10,11,11b,12,13,13a-hexadecahydrocyclopenta[a]chrysen-9-ol
• CAS: 22149-65-1
• 化学式: C₃₀H₅₂O₂
• 分子量: 444.742
• InChiKey: FNUXMEOWJVTJJE-DTXRQUTOSA-N

物化性质

• 熔点：
  284-285 °C(Solv: chloroform (67-66-3); methanol (67-56-1))
• 沸点：
  515.6±23.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  32
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

制备方法与用途

生物活性 Hopane-3β,22-二醇（化合物 74）是从 A. mariesii 中提取的一种藿烷类化合物。

反应信息

• 作为反应物：
  描述：

  hopane-3β,22-diol 在 chromium(VI) oxide 、 溶剂黄146 作用下， 以 氯仿 为溶剂， 生成 hydroxyhopanone
  参考文献：
  名称：

  Cerny,J. et al., Chemische Berichte, 1963, vol. 96, p. 3021 - 3023

  摘要：

  DOI：
• 作为产物：
  描述：

  hydroxyhopanone 在 sodium tetrahydroborate 作用下， 生成 hopane-3β,22-diol
  参考文献：
  名称：

  来自香港十种石松属的三萜类化合物

  摘要：

  摘要 来自十种石果属植物（ L. attenuata 、 L.cornea 、 L. elizabethae 、 L. glabra 、 L. haipinii 、 L. hancei 、 L. harlandi 、 L. irwinii 、 L. litchioides ）的叶和茎的石油提取物, 和 L. polystachya ), 分离出 23 种不同的三萜、谷甾醇和豆甾醇。在三萜类化合物中，有 11 种属于齐墩果烷和重排齐墩果烷组 [β-香树脂醇、弗里德林、弗里德兰-3β-醇、谷蛋白醇、蒲公英、蒲公英及其醋酸盐、树油酚​​ (28-羟基弗里德兰-3-one)、弗里德兰-2、 3-dione (3-hydroxyfriedel-3-en-2-one)、pachysandiol-A (2α,3β-dihydroxyfriedelane) 和新化合物石果酸内酯 C 30 H 50 O 2

  DOI：

  10.1016/0031-9422(75)85187-9

文献信息

• Synthesis and enzymatic cyclization of (3S)11-fluoro-2,3-oxidosqualene
  作者：Brian Robustell、Ikuro Abe、Glenn D. Prestwich

  DOI：10.1016/s0040-4039(97)10669-4

  日期：1998.2

  A convergent asymmetric synthesis provided (3S)11-fluoro-2,3-oxidosqualene (11-FOS, 14), which was cyclized by bacterial squalene:hopane cyclase to a bridged ether. 11-FOS was neither a substrate nor an inhibitor for vertebrate oxidosqualene:lanosterol cyclase.

  会聚的不对称合成提供了（3 S）11-氟-2,3-氧化角鲨烯（11-FOS，14），其被细菌角鲨烯：鹅环化酶环化成桥连醚。11-FOS既不是底物，也不是脊椎动物氧化角鲨烯：羊毛甾醇环化酶的抑制剂。
• Mutated variants of squalene-hopene cyclase: enzymatic syntheses of triterpenes bearing oxygen-bridged monocycles and a new 6,6,6,6,6-fusded pentacyclic scaffold, named neogammacerane, from 2,3-oxidosqualene
  作者：Yoriyuki Fukuda、Takashi Watanabe、Tsutomu Hoshino

  DOI：10.1039/c8ob02009d

  日期：——

  reaction have been extensively reported, but investigations of the cyclization reactions of (3R,S)-oxidosqualene by SHC have rarely been reported. The cyclization reactions of oxidosqualene with W169X, G600F/F601G and F601G/P602F were examined. The variants of the W169L generated new triterpene skeletons possessing a 7-oxabicyclo[2.2.1]heptane moiety (oxygen-bridged monocycle) with (1S,2S,4R)- and (1R,2S

  角鲨烯-戊环化酶（SHC）催化无环角鲨烯分子转化为6,6,6,6,5-稠合的五环戊烯和hop醇。SHC还能够将（3 S）-2,3-氧化角鲨烯转化为3β-羟基戊烯和3β-羟基紫杉醇，并可以从（3 R）-2,3-氧化角鲨烯生成3α-羟基戊烯和3α-羟基紫杉醇。关于角鲨烯环化反应的活性位点残基的功能分析已被广泛报道，但对（3 R，S很少报道过SHC产生的）-氧化角鲨烯。检查了氧化鲨烯与W169X，G600F / F601G和F601G / P602F的环化反应。W169L的变体生成了具有7-氧杂双环[2.2.1]庚烷部分（氧桥联的单环）的新三萜骨架，其中（1 S，2 S，4 R）-和（1 R，2 S，4 S） -立体化学，由（3 R）-和（3 S）-氧化角鲨烯。F601G / P602F双突变体还提供了一种新的三萜，名为neogammacer-21（22）-en-3β-ol，它由一个6,6,6,6
• Functional Analysis of the DXDDTA Motif in Squalene-Hopene Cyclase by Site-directed Mutagenesis Experiments: Initiation Site of the Polycyclization Reaction and Stabilization Site of the Carbocation Intermediate of the Initially Cyclized A-Ring
  作者：Tsutomu SATO、Tsutomu HOSHINO

  DOI：10.1271/bbb.63.2189

  日期：1999.1

  In order to clarify the function of the DXDDTA motif in squalene-hopene cyclase and to identify the acidic amino acid residues crucial for the catalysis, site-directed mutagenesis experiments were carried out. The following results were found: (1) residues D374 and D376 work for the initiation of polyolefin cyclization which arises from the proton attack on the terminal double bond; (2) residue D377

  为了阐明DXDDTA基序在角鲨烯-戊烯环化酶中的功能并鉴定对于催化至关重要的酸性氨基酸残基，进行了定点诱变实验。发现以下结果：（1）残基D374和D376起引发聚烯烃环化作用的作用，这是由于质子攻击末端双键而引起的；（2）残基D377稳定了最初环化的A环中间体的C-10碳正离子化，导致随后的B环封闭，这通过分离部分环化的单环产物得到了进一步证实。（3）鉴定出DXDDTA基序外的残基D313和D447为新的活性位点；（4）H451残基可能以质子化形式起作用以增强D374和/或D376的羧基的酸度。
• Kinetic Studies on the Function of All the Conserved Tryptophans Involved Inside and Outside the QW Motifs of Squalene-hopene Cyclase: Stabilizing Effect of the Protein Structure against Thermal Denaturation
  作者：Tsutomu SATO、Tsutomu HOSHINO

  DOI：10.1271/bbb.63.1171

  日期：1999.1

  Site-directed mutagenesis experiments were carried out to identify the responsibility of the eight QW motifs for the reaction catalyzed by squalene-hopene cyclase (SHC). Alterations of the conserved tryptophans, which are responsible for the stacking structure with glutamine, into aliphatic amino acids gave a significantly lower temperature for the catalytic optimum as for the mutageneses of QW motifs 4, 5a and 5b, which are specifically present in SHCs. However, there was no change in the optimal temperatures of the mutated SHCs targeted at the other five motifs 1, 2, 3, 5c and 6. Thus, reinforcement against heat denaturation can be proposed as a function of the three QW motifs 4, 5a and 5b, but no function could be identified for the QW motifs 1, 2, 3, 5c and 6, although they are commonly found in all the families of prokaryotic SHCs and eukaryotic oxidosqualene cyclases. On the other hand, the three conserved tryptophans of W169, W312 and W489, which are located inside the putative central cavity and outside the QW motifs, were identified as components of the active sites, but also had a function against thermal denaturation. The other two tryptophan residues of W142 and W558, which are located outside the QW motifs, were found not to be active sites, but also had a role for stabilizing the protein structure. It is noteworthy that the mutants replaced by phenylalanine had higher temperatures for the catalytic optimum than those replaced by aliphatic amino acids. The catalytic optimal pH values for all the mutants remained unchanged with an identical value of 6.0.

  进行定点诱变实验以确定八个 QW 基序对角鲨烯-霍烯环化酶 (SHC) 催化反应的作用。将负责与谷氨酰胺堆叠结构的保守色氨酸改变为脂肪族氨基酸，对于特别存在于 SHC 中的 QW 基序 4、5a 和 5b 的诱变，提供了显着较低的催化最佳温度。然而，针对其他五个基序 1、2、3、5c 和 6 的突变 SHC 的最佳温度没有变化。因此，可以建议将抗热变性的强化作为三个 QW 基序 4、5a 的函数。和 5b，但无法鉴定 QW 基序 1、2、3、5c 和 6 的功能，尽管它们常见于原核 SHC 和真核氧化角鲨烯环化酶的所有家族中。另一方面，位于假定的中央腔内部和QW基序外部的三个保守色氨酸W169、W312和W489被鉴定为活性位点的组成部分，但也具有抗热变性的功能。位于QW基序之外的另外两个色氨酸残基W142和W558被发现不是活性位点，但也具有稳定蛋白质结构的作用。值得注意的是，苯丙氨酸取代的突变体比脂肪族氨基酸取代的突变体具有更高的催化最佳温度。所有突变体的催化最佳pH值保持不变，均为6.0。
• <i>Alicyclobacillus acidocaldarius</i> Squalene‐Hopene Cyclase: The Critical Role of Steric Bulk at Ala306 and the First Enzymatic Synthesis of Epoxydammarane from 2,3‐Oxidosqualene
  作者：Natsumi Ideno、Shikou Umeyama、Takashi Watanabe、Mami Nakajima、Tsutomu Sato、Tsutomu Hoshino

  DOI：10.1002/cbic.201800281

  日期：2018.9.4

  SHC is widely conserved in known SHCs. Increases in steric bulk (A306T and A306V) led to the accumulation of 6,6,6,5‐fused tetracyclic scaffolds with 20R stereochemistry. This indicates folding of squalene in a chair‐chair‐chair‐boat conformation. The stereochemical fate in polycyclization is thus governed by the bulk at this position.

  Polycyclization和构象分析：Ala306在A.热硫化叶菌SHC广泛保守已知的特困家庭。空间体积（A306T和A306V）的增加导致具有20 R立体化学的6,6,6,5融合的四环支架的积累。这表明角鲨烯折叠成椅子-椅子-船构型。因此，多环化中的立体化学命运受该位置的主体支配。