2-fluoro-3,7-dimethyl-octa-2,6-dien-1-ol | 2284-91-5

• 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-fluoro-3,7-dimethyl-octa-2,6-dien-1-ol
• 英文别名: cis/trans-2-Fluor-3.7-dimethyl-Δ^2,6-octadienol-(1)；2-Fluor-geraniol；2-Fluoro-3,7-dimethylocta-2,6-dien-1-ol；2-fluoro-3,7-dimethylocta-2,6-dien-1-ol
• CAS: 2284-91-5
• 化学式: C₁₀H₁₇FO
• 分子量: 172.243
• InChiKey: XAIXQWWXQKMCFZ-UHFFFAOYSA-N

物化性质

• 沸点：
  100-101 °C(Press: 12 Torr)
• 密度：
  0.940±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-fluoro-3,7-dimethyl-octa-2,6-dien-1-ol 在 2,4,6-三甲基吡啶 、 Streptomyces coelicolor A₃⁽²⁾ 2-methylisoborneol synthase 、 (1,2-二溴-1-苯基-乙基)-膦酸 、 水 、 三乙胺 、 N,N-二异丙基乙胺 、 2-巯基乙醇 、 sodium chloride 、 magnesium chloride 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 64.0h， 生成 白樟油
  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：

  cis,trans-2-Fluor-3,7-dimethyl-Δ^2,6-octadiensaeureethylester 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 12.0h， 生成 2-fluoro-3,7-dimethyl-octa-2,6-dien-1-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

• Machleidt,H.; Wessendorf,R., Justus Liebigs Annalen der Chemie, 1964, vol. 679, p. 20 - 26
  作者：Machleidt,H.、Wessendorf,R.

  DOI：——

  日期：——
• Machleidt,H.; Wessendorf,R., Justus Liebigs Annalen der Chemie, 1964, vol. 674, p. 1 - 10
  作者：Machleidt,H.、Wessendorf,R.

  DOI：——

  日期：——
• Unexpected Reactivity of 2-Fluorolinalyl Diphosphate in the Active Site of Crystalline 2-Methylisoborneol Synthase
  作者：Mustafa Köksal、Wayne K. W. Chou、David E. Cane、David W. Christianson

  DOI：10.1021/bi400797c

  日期：2013.8.6

  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.