(S)-[1-(2)H]-3-methyl-2-buten-1-yl diphosphate | 880098-09-9

• 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: (S)-[1-(2)H]-3-methyl-2-buten-1-yl diphosphate
• 英文别名: [(1S)-1-deuterio-3-methylbut-2-enyl] phosphono hydrogen phosphate
• CAS: 880098-09-9
• 化学式: C₅H₁₂O₇P₂
• 分子量: 247.086
• InChiKey: CBIDRCWHNCKSTO-VGERMBTCSA-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：

  (S)-[1-(2)H]-3-methyl-2-buten-1-yl diphosphate 在 calf alkaline phosphatase HEPES buffer 、 2-巯基乙醇 、 magnesium chloride 、 glycine buffer 、 zinc(II) chloride 作用下， 反应 14.0h， 生成 、 (1S,1'R,3'R)-<1-²H>-Chrysanthemol
  参考文献：
  名称：

  A Common Mechanism for Branching, Cyclopropanation, and Cyclobutanation Reactions in the Isoprenoid Biosynthetic Pathway

  摘要：

  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.

  DOI：

  10.1021/ja0771282
• 作为产物：
  描述：

  3,3-二甲基丙烯酸甲酯 在 4 A molecular sieve 、 三氟乙酸 titanium(IV) isopropylate 、 lithium aluminium deuteride 、 磷酸-三乙胺 2:1 、 三正丁基氢锡 、 (R)-1,1'-Bi-2-naphthol 、 三氯乙腈 、 pyridinium chlorochromate 作用下， 以 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 31.25h， 生成 (S)-[1-(2)H]-3-methyl-2-buten-1-yl diphosphate
  参考文献：
  名称：

  Synthesis of Deuterium-Labeled Derivatives of Dimethylallyl Diphosphate

  摘要：

  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).

  DOI：

  10.1021/jo052384n

文献信息

• 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).