(3-cyclopentylidene-1,1-difluoroallyl)phosphonic acid diethyl ester

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: (3-cyclopentylidene-1,1-difluoroallyl)phosphonic acid diethyl ester
• 化学式: C₁₂H₁₉F₂O₃P
• 分子量: 280.252
• InChiKey: RKKWDCLMRMHUSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  41.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3-cyclopentylidene-1,1-difluoroallyl)phosphonic acid diethyl ester 在 sodium hydroxide 作用下， 生成 (3-cyclopentylidene-1,1-difluoroallyl)phosphonic acid monoethyl ester
  参考文献：
  名称：

  有机硫或有机硒诱导的 β-丙二烯 α-二氟亚甲基膦酸单酯的分子内环加成反应：新型环状磷酸酯模拟物的合成

  摘要：

  新型环状磷酸盐模拟物、γ-有机硫或有机硒取代的 α-二氟亚甲基膦以高产率和高区域选择性在温和条件下通过由 ArSCl 或 ArSeCl 诱导的 β-丙二烯 α-二氟亚甲基膦酸单酯的亲电环化合成。该反应代表了膦酸单酯与β-丙二烯碳-碳双键分子内加成的第一个例子。

  DOI：

  10.1055/s-2006-948204
• 作为产物：
  描述：

  溴氟甲基膦酸二乙酯 、 1-ethynylcyclopentyl acetate 在 锌 、 copper(I) bromide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以71%的产率得到(3-cyclopentylidene-1,1-difluoroallyl)phosphonic acid diethyl ester
  参考文献：
  名称：

  A facile method to construct cyclic α,α-difluoromethylenephosphonate—A novel cyclic phosphate mimic

  摘要：

  A facile and efficient synthesis of cyclic alpha,alpha-difluoromethylenephosphonates by halogen-induced intramolecular cyclization of beta-allenic alpha,alpha-difluoromethylenephosphonates is described. The protocol gives multi-substituted six-membered phosphonates with high regioselectivity, providing a new entry to the cyclic phosphate mimics which is still an unexplored but promising area. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2011.02.014

文献信息

• Organosulfur- or Organoselenium-Induced Intramolecular Cycloaddition of β-Allenic α-Difluoromethylenephosphonic Acid Monoesters: Synthesis of Novel Cyclic Phosphate Mimics
  作者：Jin-Tao Liu、Yun Lin

  DOI：10.1055/s-2006-948204

  日期：2006.9

  Novel cyclic phosphate mimics, gamma-organosulfur or organoselenium substituted alpha-difluoromethylenephostones were synthesized in good yields with high regioselectivity under mild conditions by the electrophilic cyclization of beta-allenic alpha-difluoromethylenephosphonic acid monoesters induced by ArSCl or ArSeCl. The reaction represents the first example of an intramolecular addition of phosphonic

  新型环状磷酸盐模拟物、γ-有机硫或有机硒取代的 α-二氟亚甲基膦以高产率和高区域选择性在温和条件下通过由 ArSCl 或 ArSeCl 诱导的 β-丙二烯 α-二氟亚甲基膦酸单酯的亲电环化合成。该反应代表了膦酸单酯与β-丙二烯碳-碳双键分子内加成的第一个例子。
• First iodocyclization of β-allenic phosphonates: a novel synthesis of α-difluoromethylenephostones
  作者：Yun Lin、Jin-Tao Liu

  DOI：10.1016/j.tetlet.2006.06.096

  日期：2006.8

  Six-membered alpha-difluoromethylenephostones were prepared in moderate to good yields with high regioselectivities under mild conditions from the iodocyclization reaction of diethyl beta-allenic alpha,alpha-difluorophosphonates using I-2 or ICl as the electrophile. (c) 2006 Elsevier Ltd. All rights reserved.
• A facile method to construct cyclic α,α-difluoromethylenephosphonate—A novel cyclic phosphate mimic
  作者：Yun Lin、Jin-Tao Liu

  DOI：10.1016/j.jfluchem.2011.02.014

  日期：2011.5

  A facile and efficient synthesis of cyclic alpha,alpha-difluoromethylenephosphonates by halogen-induced intramolecular cyclization of beta-allenic alpha,alpha-difluoromethylenephosphonates is described. The protocol gives multi-substituted six-membered phosphonates with high regioselectivity, providing a new entry to the cyclic phosphate mimics which is still an unexplored but promising area. (C) 2011 Elsevier B.V. All rights reserved.
• CuX 2 -mediated halocyclization of 1,1-difluoro-2,3-allenylphosphonic acid monoesters –synthesis of novel cyclic phosphate mimics
  作者：Xu Jiang、Xiang Cai、Yun Lin、Jintao Liu

  DOI：10.1016/j.tet.2018.06.058

  日期：2018.8

  2-oxaphosphinine 2-oxides) were synthesized via CuX2 (X = Br, Cl)-mediated halocyclization of 1,1-difluoro-2,3-allenylphosphonic acid monoesters in moderate to good yields with high regio-selectivity. This reaction represents the first example of transition metal-mediated intramolecular cyclization of a P-OH moiety to β-allenylphosphonates with a carbon-carbon double bond.

  通过CuX 2（X = Br，Cl）介导合成了新颖的六元环状磷酸酯模拟物（5-卤代-3,3-二氟-3,6-二氢-2 H -1,2-氧杂膦酸2-氧化物）1,1-二氟-2,3-烯丙基膦酸单酯的卤代化，具有中等至良好的收率，具有较高的区域选择性。该反应代表了过渡金属介导的P-OH部分分子间环化为具有碳-碳双键的β-烯丙基膦酸酯的第一个例子。