2-(dimethoxyphosphoryl)-1,3-dithiane | 61779-88-2

• 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: 2-(dimethoxyphosphoryl)-1,3-dithiane
• 英文别名: Dimethyl 1,3-dithian-2-ylphosphonate；2-dimethoxyphosphoryl-1,3-dithiane
• CAS: 61779-88-2
• 化学式: C₆H₁₃O₃PS₂
• 分子量: 228.273
• InChiKey: SXJWOLGZFVCYQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  86.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R,4S)-4-(dibenzylamino)-3-vinylheptanal 、 2-(dimethoxyphosphoryl)-1,3-dithiane 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.25h， 以97%的产率得到(3R,4S)-3-(2-(1,3-dithian-2-ylidene)ethyl)-N,N-dibenzylhept-1-en-4-amine
  参考文献：
  名称：

  Substrate-Controlled and Organocatalytic Asymmetric Synthesis of Carbocyclic Amino Acid Dipeptide Mimetics

  摘要：

  The asymmetric synthesis of a carbocyclic delta-amino acid representing the P-2/P-3 subunit of a nonpeptidic truncated peptidomimetic molecule is described relying on two independent approaches.

  DOI：

  10.1021/jo100017t
• 作为产物：
  描述：

  1,2-dithiolane 、 dimethyl diazomethylphosphonate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 生成 2-(dimethoxyphosphoryl)-1,3-dithiane
  参考文献：
  名称：

  Insertion of α-Phosphorylcarbene Moiety into S-S and Se-Se Bonds: Synthesis of Dithio- and Diselenoacetals of Formylphosphonates

  摘要：

  二氟肥基磷酸酯与二硫化物或二硒化物在三氟化硼-二乙醚复合物催化下发生反应，导致 (RO)2P(O)-CH(:) 基团插入 S-S 和 Se-Se 键。所提出的方法使得能够合成其他方法无法获得的 2-磷酸基取代的 1,3-二硒烷。产率取决于反应条件。还讨论了在环状体系中插入的立体选择性。由二价铑乙 acetate 或无水二价铜硫酸盐催化的反应产生相关的硫化物 (RO)2P(O)-CH2SR。提出了可能的离子和自由基机制途径。

  DOI：

  10.1055/s-1996-4355

文献信息

• 2-Dimethoxyphosphoryl-1,3-dithiane: A comparison of NMR studies for1H,13C and31P nuclei by one- and two-dimensional NMR techniques
  作者：Michael Engelhardt、Gerhard Hägele、Marian Mikolajczyk、Piotr Balczewski、Detlef Wendisch

  DOI：10.1002/mrc.1260230108

  日期：1985.1

  2-Dimethoxyphosphoryl-1,3-dithiane was obtained by the reaction of 2-chloro-1,3-dithiane with trimethyl phosphite. Studies at 200, 360 and 400 MHz using 1H, 13C and 31P nuclei and 1D- and 2D NMR techniques are described. Long-range coupling constants were extracted by iterative treatment of [AB]2CDMR6X spin systems. A rigid dithiane structure with axial phosphorus is consistent with the NMR results. Analogous dithianes and solid-state structures are discussed.

  2-Cloro-1,3-dithiane 与亚磷酸三甲酯反应生成 2-二甲氧基磷酰-1,3-二噻烷。文中介绍了使用 1H、13C 和 31P 核以及一维和二维 NMR 技术在 200、360 和 400 MHz 下进行的研究。通过对 [AB]2CDMR6X 自旋系统进行迭代处理，提取了长程耦合常数。具有轴向磷的刚性二硫环结构与核磁共振结果一致。讨论了类似的二噻烷和固态结构。
• Comparative probe for stacking interactions in simple A:T base pair mimics
  作者：David G. Lonergan、Jonathan Halse、Ghislain Deslongchamps

  DOI：10.1016/s0040-4039(98)01498-1

  日期：1998.9

  The design and synthesis of a new scaffold for the assembly of receptor models, soluble in organic solvent, is described. It was converted into a simple receptor for 9-butyladenine and compared to other isosteric AT base pair mimics. The results support the Sanders and Hunter pi-stacking model. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Insertion of α-Phosphorylcarbene Moiety into S-S and Se-Se Bonds: Synthesis of Dithio- and Diselenoacetals of Formylphosphonates
  作者：M. Mikołajczyk、M. Mikina、P. P. Graczyk、P. Bałczewski

  DOI：10.1055/s-1996-4355

  日期：1996.10

  Reaction between diazomethanephosphonates and disulfides or diselenides catalyzed by boron trifluoride - diethyl ether complex leads to insertion of the (RO)2P(O)-CH(:) moiety into S-S and Se-Se bonds, respectively. The proposed method makes it possible to synthesize 2-phosphoryl-substituted 1,3-diselenanes, not available by other means. The yield depends on the reaction conditions. Stereoselectivity of insertion into cyclic systems is discussed. Reactions catalyzed by rhodium(II) acetate or anhydrous copper(II) sulfate afford the relevant sulfides, (RO)2P(O)-CH2SR. The possible ionic and free radical mechanistic pathways are presented.

  二氟肥基磷酸酯与二硫化物或二硒化物在三氟化硼-二乙醚复合物催化下发生反应，导致 (RO)2P(O)-CH(:) 基团插入 S-S 和 Se-Se 键。所提出的方法使得能够合成其他方法无法获得的 2-磷酸基取代的 1,3-二硒烷。产率取决于反应条件。还讨论了在环状体系中插入的立体选择性。由二价铑乙 acetate 或无水二价铜硫酸盐催化的反应产生相关的硫化物 (RO)2P(O)-CH2SR。提出了可能的离子和自由基机制途径。
• Substrate-Controlled and Organocatalytic Asymmetric Synthesis of Carbocyclic Amino Acid Dipeptide Mimetics
  作者：Stephen Hanessian、Dilip K. Maji、Subramaniyan Govindan、Riccardo Matera、Marina Tintelnot-Blomley

  DOI：10.1021/jo100017t

  日期：2010.5.7

  The asymmetric synthesis of a carbocyclic delta-amino acid representing the P-2/P-3 subunit of a nonpeptidic truncated peptidomimetic molecule is described relying on two independent approaches.