(±)-2-fluoro-3,7-dimethylocta-1,6-dien-3-ol | 64031-55-6

• 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-fluoro-3,7-dimethylocta-1,6-dien-3-ol
• 英文别名: 2-fluorolinalool；(±)-2-fluorolinalool；2-fluoro-3,7-dimethyl-octa-1,6-dien-3-ol；2-Fluor-3,7-dimethyl-1,6-octadien-3-ol；2-fluoro-3,7-dimethylocta-1,6-dien-3-ol
• CAS: 64031-55-6
• 化学式: C₁₀H₁₇FO
• 分子量: 172.243
• InChiKey: IXINRQTXXGARKH-UHFFFAOYSA-N

物化性质

• 沸点：
  235.6±40.0 °C(Predicted)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.97
• 重原子数：
  12.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (±)-2-fluoro-3,7-dimethylocta-1,6-dien-3-ol 在 lithium aluminium tetrahydride 、 Streptomyces coelicolor A₃⁽²⁾ 2-methylisoborneol synthase 、 (1,2-二溴-1-苯基-乙基)-膦酸 、 N,N-二异丙基乙胺 、 2-巯基乙醇 、 sodium chloride 、 magnesium chloride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 60.5h， 生成 1,7,7-三甲基双环[2.2.1]庚烷-2-醇
  参考文献：
  名称：

  Unexpected Reactivity of 2-Fluorolinalyl Diphosphate in the Active Site of Crystalline 2-Methylisoborneol Synthase

  摘要：

  The crystal structure of 2-methylisoborneol synthase (MIBS) from Streptomyces coelicolor A3(2) has been determined in its unliganded state and in complex with two Mg2+ ions and 2-fluoroneryl diphosphate at 1.85 and 2.00 angstrom resolution, respectively. Under normal circumstances, MIBS catalyzes the cyclization of the naturally occurring, noncanonical 11-carbon isoprenoid substrate, 2-methylgeranyl diphosphate, which first undergoes an ionization-somerization-ionization sequence through the tertiary diphosphate intermediate 2-methyllinalyl diphosphate to enable subsequent cyclization chemistry. MIBS does not exhibit catalytic activity with 2-fluorogeranyl cliphosphate, and we recently reported the crystal structure of MIBS complexed with this unreactive substrate analogue [Koksal, M., Chou, W. K. W., Cane, D. E., Christianson, D. W. (2012) Biochemistry SI, 3011-3020]. However, cocrystallization of MIBS with the fluorinated analogue of the tertiary allylic diphosphate intermediate, 2-fluorolinalyl diphosphate, reveals unexpected reactivity for the intermediate analogue and yields the crystal structure of the complex with the primary allylic diphosphate, 2-fluoroneryl diphosphate. Comparison with the structure of the unliganded enzyme reveals that the crystalline enzyme active site remains partially open, presumably due to the binding of only two Mg2+ ions. Assays in solution indicate that MIBS catalyzes the generation of (1R)-(+)-camphor from the substrate 2-fluorolinalyl diphosphate, suggesting that both 2-fluorolinalyl diphosphate and 2-fluorolinalyl diphosphate follow the identical cyclization mechanism leading to 2-substituted isobomeol products; however, the initially generated 2-fluoroisoborneol cyclization product is unstable and undergoes elimination of hydrogen fluoride to yield (1R)-(+)-camphor.

  DOI：

  10.1021/bi400797c
• 作为产物：
  描述：

  2-fluoro-3,7-dimethyl-octa-2,6-dien-1-ol 在 2,4,6-三甲基吡啶 、 水 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 4.0h， 生成 (±)-2-fluoro-3,7-dimethylocta-1,6-dien-3-ol
  参考文献：
  名称：

  Unexpected Reactivity of 2-Fluorolinalyl Diphosphate in the Active Site of Crystalline 2-Methylisoborneol Synthase

  摘要：

  The crystal structure of 2-methylisoborneol synthase (MIBS) from Streptomyces coelicolor A3(2) has been determined in its unliganded state and in complex with two Mg2+ ions and 2-fluoroneryl diphosphate at 1.85 and 2.00 angstrom resolution, respectively. Under normal circumstances, MIBS catalyzes the cyclization of the naturally occurring, noncanonical 11-carbon isoprenoid substrate, 2-methylgeranyl diphosphate, which first undergoes an ionization-somerization-ionization sequence through the tertiary diphosphate intermediate 2-methyllinalyl diphosphate to enable subsequent cyclization chemistry. MIBS does not exhibit catalytic activity with 2-fluorogeranyl cliphosphate, and we recently reported the crystal structure of MIBS complexed with this unreactive substrate analogue [Koksal, M., Chou, W. K. W., Cane, D. E., Christianson, D. W. (2012) Biochemistry SI, 3011-3020]. However, cocrystallization of MIBS with the fluorinated analogue of the tertiary allylic diphosphate intermediate, 2-fluorolinalyl diphosphate, reveals unexpected reactivity for the intermediate analogue and yields the crystal structure of the complex with the primary allylic diphosphate, 2-fluoroneryl diphosphate. Comparison with the structure of the unliganded enzyme reveals that the crystalline enzyme active site remains partially open, presumably due to the binding of only two Mg2+ ions. Assays in solution indicate that MIBS catalyzes the generation of (1R)-(+)-camphor from the substrate 2-fluorolinalyl diphosphate, suggesting that both 2-fluorolinalyl diphosphate and 2-fluorolinalyl diphosphate follow the identical cyclization mechanism leading to 2-substituted isobomeol products; however, the initially generated 2-fluoroisoborneol cyclization product is unstable and undergoes elimination of hydrogen fluoride to yield (1R)-(+)-camphor.

  DOI：

  10.1021/bi400797c

文献信息

• Alternative Synthesis of the Colorado Potato Beetle Pheromone
  作者：Juan A. Faraldos、Robert M. Coates、José-Luis Giner

  DOI：10.1021/jo4017056

  日期：2013.10.18

  involves a 6-endo epoxide ring-opening with ester participation that simultaneously inverts the 3R-configuration of the (3R)-2,3-epoxy-2-fluoroprenyl acetate intermediate and installs the ketone functionality of the semiochemical. Extensive NMR studies validate the proposed 6-endo mechanism of the featured rearrangement, which under anhydrous conditions resulted in the formation of two bicyclic 1,3-dioxan-5-ones

  雄性科罗拉多马铃薯甲虫分泌的信息素的简明制剂[即。(3 S )-1,3-二羟基-3,7-二甲基-6-辛烯-2-one]从2-氟橙花醇或2-氟香叶醇开始，分四步完成。合成中的关键步骤涉及酯参与的 6-内环氧化物开环，同时反转(3 R )-2,3-环氧-2-氟异戊二烯乙酸酯中间体的 3 R-构型并安装符号化学。广泛的 NMR 研究验证了所提出的特征重排的 6-endo 机制，该机制在无水条件下通过前所未有的分子内 Prins 环化形成两个双环 1,3-二恶烷-5-酮。
• Solvolytic Ring-opening of Alkoxychlorofluorocyclopropanes: A Ready Access to Fluorinated α,β-Unsaturated Aldehydes and Ketones
  作者：Yvonne Bessière、Dang Ngoc-Huê Savary、Manfred Schlosser

  DOI：10.1002/hlca.19770600528

  日期：1977.7.13

  Alkoxychlorofluorocyclopropanes are easily prepared by chlorofluorocarbene addition to en-ethers in a two-phase system and converted by simple heating in an aqueous solvent mixture to 2-fluoro-2-alkenals which can be reduced to the corresponding alcohols.

  烷氧基氯氟环丙烷很容易通过在两相体系中将氯氟卡宾加成至醚中来制备，并通过在水性溶剂混合物中简单加热而转化为2-氟-2-烯基，该2-氟-2-烯基可以还原为相应的醇。
• Model studies of terpene biosynthesis. A stepwise mechanism for cyclization of nerol to .alpha.-terpineol
  作者：C. Dale Poulter、Chi Hsin R. King

  DOI：10.1021/ja00369a046

  日期：1982.3