((4-methylfuran-2-yl)methyl)phosphonic acid | 1564261-09-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: ((4-methylfuran-2-yl)methyl)phosphonic acid
• CAS: 1564261-09-1
• 化学式: C₆H₉O₄P
• 分子量: 176.109
• InChiKey: JXKLGUBDQYFNQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.27
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  70.67
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  diethyl (4-(((tert-butyldimethylsilyl)oxy)methyl)-2-oxopent-4-en-1-yl)phosphonate 在 三甲基溴硅烷 、 三氟乙酸 、 烯丙基三甲基硅烷 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 ((4-methylfuran-2-yl)methyl)phosphonic acid
  参考文献：
  名称：

  Mechanistic Consequences of Chiral Radical Clock Probes: Analysis of the Mononuclear Non-Heme Iron Enzyme HppE with 2-Hydroxy-3-methylenecyclopropyl Radical Clock Substrates

  摘要：

  (S)-2-Hydroxypropylphosphonic acid [(S)-HPP] epoxidase (HppE) is a mononuclear iron enzyme that catalyzes the last step in the biosynthesis of the antibiotic fosfomycin. HppE also processes the (R)enantiomer of H PP but converts it to 2-oxo-propylphosphonic acid. In this study, all four stereoisomers of 3-methylenecyclopropyl-containing substrate analogues, (2R, 3R)-8, (2R, 3S)-8, (2S, 3R)-8, and (2S, 3S)-8, were synthesized and used as radical probes to investigate the mechanism of the HppE-catalyzed reaction. Upon treatment with HppE, (2S, 3R)-8 and (2S, 3S)-8 were converted via a Cl radical intermediate to the corresponding epoxide products, as anticipated. In contrast, incubation of HppE with (2R, 3R)-8 led to enzyme inactivation, and incubation of HppE with (2R, 3S)-8 yielded the 2-keto product. The former finding is consistent with the formation of a C2 radical intermediate, where the inactivation is likely triggered by radical-induced ring cleavage of the methylenecyclopropyl group. Reaction with (2R, 3S)-8 is predicted to also proceed via a C2 radical intermediate, but no enzyme inactivation and no ring-opened product were detected. These results strongly suggest that an internal electron transfer to the iron center subsequent to C H homolysis competes with ring-opening in the processing of the C2 radical intermediate. The different outcomes of the reactions with (2R, 3R)-8 and (2R, 3S)-8 demonstrate the need to carefully consider the chirality of substituted cyclopropyl groups as radical reporting groups in studies of enzymatic mechanisms.

  DOI：

  10.1021/ja4100035