(2E,6E)-<6-2H>-farnesyl diphosphate | 168001-74-9

• 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: (2E,6E)-<6-2H>-farnesyl diphosphate
• 英文别名: (2E,6E)-<6-²H>-farnesyl diphosphate；<6-H2>farnesyl diphosphate；[6-H2]farnesyl diphosphate
• CAS: 168001-74-9
• 化学式: C₁₅H₂₈O₇P₂
• 分子量: 383.323
• InChiKey: VWFJDQUYCIWHTN-DNUJTHPOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  24.0
• 可旋转键数：
  11.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  113.29
• 氢给体数：
  3.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2E,6E)-<6-2H>-farnesyl diphosphate 在 phomopsene synthase 作用下， 生成 phomopsene
  参考文献：
  名称：

  磷萜合酶的环化机理：基于质谱的各种位点特异性标记的萜烯的分析。

  摘要：

  阐明萜烯合酶催化的环化机制对于合理设计萜烯环化酶很重要。我们开发了一种化学酶法，用于合成系统化的氘标记的香叶基香叶基二磷酸酯（GGPP），从使用IPP异构酶和三种异戊二烯基转移酶的位点特异性氘标记的异戊烯基二磷酸酯（IPP）开始。我们研究了四环二萜磷杂环戊烯与磷杂环戊烯合酶的环化机理。对在各个位置标记的磷杂环戊烯进行的详细EI-MS分析使我们能够提出对应于最强峰的结构，从而阐明了通过dolabelladien涉及双1,2-烷基转移和1,2-氢化物转移的环化机理-15-阳离子。

  DOI：

  10.1038/ja.2017.27
• 作为产物：
  描述：

  5-甲基-4-己烯酸乙酯 在 lithium aluminium tetrahydride 、 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 6.67h， 生成 (2E,6E)-<6-2H>-farnesyl diphosphate
  参考文献：
  名称：

  Biosynthesis of (+)-epicubenol

  摘要：

  Incubation of [6-H-2]FPP (14a) with epicubenol synthase isolated from Streptomyces sp. LL-B7 gave epicubenol (1c) labeled at D-9 as established by 2H NMR. These results confirm the involvement of a predicted 1,2-hydride shift in the mechanism of formation of 1.

  DOI：

  10.1016/s0040-4039(00)73498-8

文献信息

• A 1,6-Ring Closure Mechanism for (+)-δ-Cadinene Synthase?
  作者：Juan A. Faraldos、David J. Miller、Verónica González、Zulfa Yoosuf-Aly、Oscar Cascón、Amang Li、Rudolf K. Allemann

  DOI：10.1021/ja211820p

  日期：2012.4.4

  Recombinant (+)-delta-cadinene synthase (DCS) from Gossypium arboreum catalyzes the metal-dependent cyclization of (E,E)-farnesyl diphosphate (FDP) to the cadinane sesquiterpene delta-cadinene, the parent hydrocarbon of cotton phytoalexins such as gossypol. In contrast to some other sesquiterpene cyclases, DCS carries out this transformation with >98% fidelity but, as a consequence, leaves no mechanistic traces of its mode of action. The formation of (+)-delta-cadinene has been shown to occur via the enzyme-bound intermediate (3R)-nerolidyl diphosphate (NDP), which in turn has been postulated to be converted to cis-germacradienyl cation after a 1,10-cyclization. A subsequent 1,3-hydride shift would then relocate the carbocation within the transient macrocycle to expedite a second cyclization that yields the cadinenyl cation with the correct cis stereochemistry found in (+)-delta-cadinene. An elegant 1,10-mechanistic pathway that avoids the formation of (3R)-NDP has also been suggested. In this alternative scenario, the final cadinenyl cation is proposed to be formed through the intermediacy of trans, trans-germacradienyl cation and germacrene D. In addition, an alternative 1,6-ring closure mechanism via the bisabolyl cation has previously been envisioned. We report here a detailed investigation of the catalytic mechanism of DCS using a variety of mechanistic probes including, among others, deuterated and fluorinated FDPs. Farnesyl diphosphate analogues with fluorine at C2 and C10 acted as inhibitors of DCS, but intriguingly, after prolonged overnight incubations, they yielded 2F-germacrene(s) and a 10F-humulene, respectively. The observed 1,10-, and to a lesser extent, 1,11-cyclization activity of DCS with these fluorinated substrates is consistent with the postulated macrocyclization mechanism(s) en route to (+)-delta-cadinene. On the other hand, mechanistic results from incubations of DCS with 6F-FPP, (2Z,6E)-FDP, neryl diphosphate, 6,7-dihydro-FDP, and NDP seem to be in better agreement with the potential involvement of the alternative biosynthetic 1,6-ring closure pathway. In particular, the strong inhibition of DCS by 6F-FDP, coupled to the exclusive bisabolyl- and terpinyl-derived product profiles observed for the DCS-catalyzed turnover of (2Z,6E)-farnesyl and neryl diphosphates, suggested the intermediacy of alpha-bisabolyl cation. DCS incubations with enantiomerically pure [1-H-2(1)](1R)-FDP revealed that the putative bisabolyl-derived 1,6-pathway proceeds through (3R)-nerolidyl diphosphate (NDP), is consistent with previous deuterium-labeling studies, and accounts for the cis stereochemistry characteristic of cadinenyl-derived sesquiterpenes. While the results reported here do not unambiguously rule in favor of 1,6- or 1,10-cyclization, they demonstrate the mechanistic versatility inherent to DCS and highlight the possible existence of multiple mechanistic pathways.
• Biosynthesis of (+)-cubenene and (+)-epicubenol by cell-free extracts of cultured cells of Heteroscyphus planus and cyclization of [2H]farnesyl diphosphates
  作者：Kensuke Nabeta、Kazuyoshi Kigure、Masaru Fujita、Tomomi Nagoya、Takehiro Ishikawa、Hiroshi Okuyama、Toshihide Takasawa

  DOI：10.1039/p19950001935

  日期：——

  The absolute stereochemistry of cubenene and epicubenol from cultured cells of Heteroscyphus planus was determined as both (+)-isomers by H-1 and C-13 NMR spectroscopy, GLC using a chiral capillary column, and optical rotations. Incubation of two geometrical isomers of deuteriated farnesyl diphosphate (FPP) with a cell-free extract from cultured cells indicated that both compounds were specifically formed from (2E,6E)-FPP. Gas-liquid chromatography-mass spectrometry (GLC-MS) and H-2 NMR analyses of(+)-cubenene and (+)-epicubenol generated from [1,1-H-2(2)]- and [6-H-2]-FPP confirmed the presence of 1,2- and 1,3-hydride shifts in their formation.
• Effect of Isotopically Sensitive Branching on Product Distribution for Pentalenene Synthase: Support for a Mechanism Predicted by Quantum Chemistry
  作者：Liansuo Zu、Meimei Xu、Michael W. Lodewyk、David E. Cane、Reuben J. Peters、Dean J. Tantillo

  DOI：10.1021/ja3043245

  日期：2012.7.18

  Mechanistic proposals for the carbocation cascade reaction leading to the tricyclic sesquiterpene pentalenene are assessed in light of the results of isotopically sensitive branching experiments with the H309A mutant of pentalenene synthase. These experimental results support a mechanism for pentalenene formation involving a 7-protoilludyl cation whose intermediacy was first predicted using quantum-chemical calculations.