[2-(2)H]-3-methyl-2-butenyl diphosphate | 880098-13-5

• 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: [2-(2)H]-3-methyl-2-butenyl diphosphate
• 英文别名: (2-Deuterio-3-methylbut-2-enyl) phosphono hydrogen phosphate
• CAS: 880098-13-5
• 化学式: C₅H₁₂O₇P₂
• 分子量: 247.086
• InChiKey: CBIDRCWHNCKSTO-WFVSFCRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  113
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [2-(2)H]-3-methyl-2-butenyl diphosphate 在 geranylgeranyl pyrophosphate synthase from Streptomyces cyaneofuscatus 、 spiroalbatene synthase 作用下， 以 aq. buffer 为溶剂， 反应 6.0h， 生成
  参考文献：
  名称：

  两种来自Alkutzneria albata的螺二烯和Cembrene A的二萜合酶

  摘要：

  研究了来自放线放线菌变种Allokutzneria albata的两种细菌二萜合酶，从而鉴定出结构上前所未有的第一种酶化合物螺螺丙烯和第二种酶的西em烯A。通过同位素标记实验，定点诱变以及金属辅因子和pH值的变化，对这两种酶的机理进行了彻底研究。对于螺碳巴烯合酶，观察到副产物丁保酚的pH和Mn 2+依赖性形成，其与螺碳巴烯生物合成相连。

  DOI：

  10.1002/anie.201800385
• 作为产物：
  描述：

  ethyl [2-(2)H]-3-methyl-2-butenoate 在 三溴化磷 、 二异丁基氢化铝 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 [2-(2)H]-3-methyl-2-butenyl diphosphate
  参考文献：
  名称：

  Phomactin 血小板激活因子拮抗剂的生物合成需要双酶级联

  摘要：

  自然界中多种福玛汀的形成只需要两种酶：I型二萜环化酶PhmA和P450单加氧酶PhmC。PhmA 催化 GGPP 转化为 phomactatriene，而 PhmC 以顺序方式协调 phomactatriene 内多个位点的氧化。这种精细协调的酶级联最终导致产生一系列令人着迷的结构多样的福马汀。

  DOI：

  10.1002/anie.202312996

文献信息

• Mechanisms of the Diterpene Cyclases β-Pinacene Synthase from<i>Dictyostelium discoideum</i>and Hydropyrene Synthase from<i>Streptomyces clavuligerus</i>
  作者：Jan Rinkel、Patrick Rabe、Xinlu Chen、Tobias G. Köllner、Feng Chen、Jeroen S. Dickschat

  DOI：10.1002/chem.201702704

  日期：2017.8.4

  Two diterpene cyclases, one from the social amoeba Dictyostelium discoideum and the other from the bacterium Streptomyces clavuligerus, with products containing a Z‐configured double bond between the original C2 and C3 of geranylgeranyl diphosphate, were extensively investigated for their mechanisms through isotopic labelling experiments. The participation of geranyllinalyl diphosphate, in analogy

  两种双萜环化酶，一种来自社交变形虫盘基网柄菌，另一种来自细菌链霉菌，其产物在二磷酸香叶基香叶基二磷酸的原始C2和C3之间含有Z构型的双键，通过同位素标记实验对其机理进行了广泛研究。讨论了草甘膦基二磷酸二酯的参与，类似于芳基二磷酸和神经节苷脂在单萜和倍半萜生物合成中的作用，它是形成具有Z构型的C2 = C3双键的二萜的中间体。
• A Branched Diterpene Cascade: The Mechanism of Spinodiene Synthase from<i>Saccharopolyspora spinosa</i>
  作者：Jan Rinkel、Lukas Lauterbach、Jeroen S. Dickschat

  DOI：10.1002/anie.201812216

  日期：2019.1.8

  synthase from Saccharopolyspora spinosa was found to convert geranylgeranyl diphosphate into the new natural products spinodiene A and B, accompanied by 2,7,18‐dolabellatriene. The structures and the formation mechanism of the enzyme products were investigated by extensive isotopic labelling experiments, which revealed an unusual branched isomerisation mechanism towards the neutral intermediate 2,7,18‐dolabellatriene

  从二萜合酶糖多孢菌中发现转换香叶基二磷酸到新的天然产品spinodiene A和B，伴随着2,7,18-dolabellatriene。通过广泛的同位素标记实验研究了酶产物的结构和形成机理，揭示了一种向中性中间体2,7,18-dolabellatriene的不寻常的分支异构化机理。Diels-Alder反应用于将主要的二萜产物及其稀有的共轭二烯部分转化为正式的酯基萜烯醇。
• A Common Mechanism for Branching, Cyclopropanation, and Cyclobutanation Reactions in the Isoprenoid Biosynthetic Pathway
  作者：Hirekodathakallu V. Thulasiram、Hans K. Erickson、C. Dale Poulter

  DOI：10.1021/ja0771282

  日期：2008.2.1

  Four reactions-chain elongation, cyclopropanation, branching, and cyclobutanation-are used in nature to join isoprenoid units for construction of the carbon skeletons for over 55 000 naturally occurring isoprenoid compounds. Those molecules produced by chain elongation have head-to-tail (regular) carbon skeletons, while those from cyclopropanation, branching, or cyclobutanation have non-head-to-tail (irregular) skeletons. Although wild type enzymes have not been identified for the branching and cyclobutanation reactions, chimeric proteins constructed from farnesyl diphosphate synthase (chain elongation) and chrysanthemyl diphosphate synthase (cyclopropanation) catalyze all four of the known isoprenoid coupling reactions to give a mixture of geranyl diphosphate (chain elongation), chrysanthemyl diphosphate (cyclopropanation), lavandulyl diphosphate (branching), and maconelliyl and planococcyl diphosphate (cyclobutanation). Replacement of the hydrogen atoms at C1 or C2 or hydrogen atoms in the methyl groups of dimethylallyl diphosphate by deuterium alters the distribution of the cyclopropanation, branching, and cyclobutanation products through primary and secondary kinetic isotope effects on the partitioning steps of common carbocationic intermediates. These experiments establish the sequence in which the intermediates are formed and indicate that enzyme-mediated control of the carbocationic rearrangement and elimination steps determines the distribution of products.
• Synthesis of Deuterium-Labeled Derivatives of Dimethylallyl Diphosphate
  作者：Hirekodathakallu V. Thulasiram、Richard M. Phan、Susan B. Rivera、C. Dale Poulter

  DOI：10.1021/jo052384n

  日期：2006.2.1

  Short practical syntheses for five deuterium-labeled derivatives of dimethylallyl diphosphate (DMAPP) useful for enzymological studies are reported. These include the preparation of the Cl-labeled derivatives (R)-[1-H-2]3-methylbut-2-enyl diphosphate ((R)-[1-H-2]1-OPP) and (S)-[1-H-2]3-methylbut-2-enyl diphosphate ((S)-[1-H-2]1-OPP), the C2-labeled derivative [2-H-2]3-methylbut-2-enyl diphosphate ([2-H-2]1-OPP), and the methyl-labeled derivatives (E)-[4,4,4-H-2(3)]3-methylbut-2-enyl diphosphate ((E)-[4,4,4-H-2(3)]1-OPP) and (Z)-[4,4,4-H-2(3)]3-methyl-but-2-enyl diphosphate ((Z)[4,4,4-H-2(3)]1-OPP).