ethyl 3,7-dimethyl-<2-2H>octa-2,6-dienoate | 168001-72-7

• 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: ethyl 3,7-dimethyl-<2-2H>octa-2,6-dienoate
• 英文别名: ethyl 3,7-dimethyl-<2-²H>octa-2,6-dienoate；ethyl 3,7-dimethyl-2,6-octadienoate；ethyl 3,7-dimethyl-[2-²H]octa-2,6-dienoate
• CAS: 168001-72-7
• 化学式: C₁₂H₂₀O₂
• 分子量: 197.282
• InChiKey: ZPKNTCZTABQJPS-QOWOAITPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  14.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ethyl 3,7-dimethyl-<2-2H>octa-2,6-dienoate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 以45%的产率得到(2E)-[2-²H₁]-3,7-dimethylocta-2,6-dien-1-ol
  参考文献：
  名称：

  Colletotrichum gloeosporioides的Clade II-D真菌嵌合二萜合酶产生Dolasta-1（15），8-diene

  摘要：

  基于酵母中的类萜过量生产平台用于基因组挖掘，来自内生真菌Colletotrichum gloeosporioides ES026的嵌合二萜合酶被表征为（5 R，12 R，14 S）-dolasta-1（15），8-二烯合酶。绝对构型通过使用对映选择性氘化的萜烯前体独立验证，该前体明确为这种第一个表征的II-D进化酶建立了预测的C1-III-IV环化模式。广泛的同位素标记实验和中间（1 R）-δ-芳烃的分离支持了所提出的环化机理。

  DOI：

  10.1002/anie.201809954
• 作为产物：
  描述：

  Ethyl 2,2-dideuterio-3-hydroxy-3,7-dimethyloct-6-enoate 在 三氯氧磷 作用下， 以 吡啶 为溶剂， 反应 72.0h， 生成 ethyl 3,7-dimethyl-<2-2H>octa-2,6-dienoate
  参考文献：
  名称：

  Biosynthesis of (+)-cubenene and (+)-epicubenol by cell-free extracts of cultured cells of Heteroscyphus planus and cyclization of [2H]farnesyl diphosphates

  摘要：

  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.

  DOI：

  10.1039/p19950001935

文献信息

• Characterization and Engineering of Two Highly Paralogous Sesquiterpene Synthases Reveal a Regioselective Reprotonation Switch
  作者：Dan Ye、Yi‐Zhen Shao、Wen‐Rui Li、Zhen‐Jia Cui、Ting Gong、Jin‐Ling Yang、Hai‐Qiang Wang、Jun‐Gui Dai、Ke‐Ping Feng、Ming Ma、Shuang‐Gang Ma、Yun‐Bao Liu、Ping Zhu、Shi‐Shan Yu

  DOI：10.1002/anie.202315674

  日期：2024.3.22

  Sesquiterpene synthases (STPSs) catalyze carbocation‐driven cyclization reactions that can generate structurally diverse hydrocarbons. The deprotonation‐reprotonation process is widely used in STPSs to promote structural diversity, largely attributable to the distinct regio/stereoselective reprotonations. However, the molecular basis for reprotonation regioselectivity remains largely understudied. Herein, we analyzed two highly paralogous STPSs, Artabotrys hexapetalus (−)‐cyperene synthase (AhCS) and ishwarane synthase (AhIS), which catalyze reactions that are distinct from the regioselective protonation of germacrene A (GA), resulting in distinct skeletons of 5/5/6 tricyclic (−)‐cyperene and 6/6/5/3 tetracyclic ishwarane, respectively. Isotopic labeling experiments demonstrated that these protonations occur at C3 and C6 of GA in AhCS and AhIS, respectively. The cryo‐electron microscopy‐derived AhCS complex structure provided the structural basis for identifying different key active site residues that may govern their functional disparity. The structure‐guided mutagenesis of these residues resulted in successful functional interconversion between AhCS and AhIS, thus targeting the three active site residues [L311‐S419‐C458]/[M311‐V419‐A458] that may act as a C3/C6 reprotonation switch for GA. These findings facilitate the rational design or directed evolution of STPSs with structurally diverse skeletons.