2,2,3-trimethyl-1-phenylphosphetane | 16083-97-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2,3-trimethyl-1-phenylphosphetane
• 英文别名: 2,2,3-trimethyl-1-phenyl-phosphetane；2,2,3-Trimethyl-1-phenylphosphetane
• CAS: 16083-97-9
• 化学式: C₁₂H₁₇P
• 分子量: 192.241
• InChiKey: HFJYHBJRPNMOGG-UHFFFAOYSA-N

物化性质

• 沸点：
  260.1±7.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,2,3-trimethyl-1-phenylphosphetane 在 四氟硼酸-二乙醚络合物 作用下， 以 乙醚 为溶剂， 反应 0.5h， 以81%的产率得到2,2,3-trimethyl-1-phenylphosphetanium tetrafluoroborate
  参考文献：
  名称：

  Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via P^III/P^VRedox Cycling

  摘要：

  We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic, evidence supports the formation of a penta:coordinate (sigma(5)-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular docomposition of the sigma(5)-P hydridophosphorane via a conceited cyclic transition,structure that delivers the observed allylic transposition and completes a novel P-III/P-V redox Catalytic cycle. These results broaden the growing repertoire., of reactions catalyzed within the P-III/P-V redox couple and suggest additional opportunities for organophosphorus,catalysis in a biphilic mode.

  DOI：

  10.1021/jacs.5b01899

文献信息

• Further ring openings and ring expansions of phosphetans
  作者：J. R. Corfield、M. J. P. Harger、J. R. Shutt、S. Trippett

  DOI：10.1039/j39700001855

  日期：——

  4-hexamethyl-1-phenylphosphetanium iodide led to ring opening via pentacovalent intermediates as also did the action of cyanide ion on this salt. Ring expansions of 2,2,3-trimethyl- and 2,2,3,3-tetramethyl-1-phenylphosphetan on reaction with ethyl propiolate in wet ether, on reaction with dimethyl acetylenedicarboxylate, and on hydrolysis of the iodomethylphosphetanium salts, occur with migration of the

  描述了磷脂的其他开环和扩环。试图由1,2,2,3,4,4-六甲基-1-苯基碘化碘生成内鎓盐导致经由五价中间体的开环，氰化物离子对该盐的作用也是如此。与2,2,3-三甲基和2,2,3,3-四甲基-1-苯基磷杂环丁酮在湿醚中与丙酸乙酯反应，与乙炔二羧酸二甲酯反应，以及碘甲基磷鎓盐水解时发生扩环。亚甲基和/或异亚丙基的迁移。2,2,3-Trimethyl-和2,2,3,3-tetramethyl-1-phenylphosphetan氧化物容易被稀碱水解，并具有开环作用，得到次膦酸。
• Preparation and chemistry of some cyclic phosphoranes
  作者：D. B. Denney、D. Z. Denney、C. D. Hall、K. L. Marsi

  DOI：10.1021/ja00756a043

  日期：1972.1
• Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via P^III/P^VRedox Cycling
  作者：Kyle D. Reichl、Nicole L. Dunn、Nicholas J. Fastuca、Alexander T. Radosevich

  DOI：10.1021/jacs.5b01899

  日期：2015.4.29

  We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic, evidence supports the formation of a penta:coordinate (sigma(5)-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular docomposition of the sigma(5)-P hydridophosphorane via a conceited cyclic transition,structure that delivers the observed allylic transposition and completes a novel P-III/P-V redox Catalytic cycle. These results broaden the growing repertoire., of reactions catalyzed within the P-III/P-V redox couple and suggest additional opportunities for organophosphorus,catalysis in a biphilic mode.