2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2-diazaphospholidine | 704890-52-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2-diazaphospholidine
• 英文别名: (4S,5S)-2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2-diazaphospholidine
• CAS: 704890-52-8
• 化学式: C₁₆H₁₈ClN₂P
• 分子量: 304.759
• InChiKey: YKWGQAACTGDWFM-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6,6'-dimethyl-2,2'-biphenyldiol 、 2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2-diazaphospholidine 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 作用下， 生成 (4S,5S)-2-[2-[2-[[(4S,5S)-1,3-dimethyl-4,5-diphenyl-2-sulfanylidene-1,3,2λ5-diazaphospholidin-2-yl]oxy]-6-methylphenyl]-3-methylphenoxy]-1,3-dimethyl-4,5-diphenyl-2-sulfanylidene-1,3,2λ5-diazaphospholidine
  参考文献：
  名称：

  Determination of enantiomeric purity of hydroxy biaryls using 1H and 31P-NMR on their diazaphospholidine derivatives

  摘要：

  Chiral biaryl alcohols were readily transformed in a single step, with chiral nonracemic 1,2-diamines, PCl3, and sulfur in CDCl3 - all in a NMR tube - to their diastereomeric diazaphospholidines and their diastereomeric ratios (also ee's) assessed directly.

  DOI：

  10.1016/s0040-4039(00)77044-4
• 作为产物：
  描述：

  (1R,2R)-N,N'-二甲基-1,2-二苯基-1,2-乙二胺 在 N,N-二乙基苯胺 、 三氯化磷 作用下， 以 氘代氯仿 为溶剂， 生成 2-chloro-1,3-dimethyl-4,5-diphenyl-1,3,2-diazaphospholidine
  参考文献：
  名称：

  Determination of enantiomeric purity of hydroxy biaryls using 1H and 31P-NMR on their diazaphospholidine derivatives

  摘要：

  Chiral biaryl alcohols were readily transformed in a single step, with chiral nonracemic 1,2-diamines, PCl3, and sulfur in CDCl3 - all in a NMR tube - to their diastereomeric diazaphospholidines and their diastereomeric ratios (also ee's) assessed directly.

  DOI：

  10.1016/s0040-4039(00)77044-4

文献信息

• Synthesis, resolution, and application of 2,2′-bis(diphenylphosphino)-3,3′-binaphtho[<i>b</i>]furan (BINAPFu)
  作者：Neil G Andersen、Masood Parvez、Robert McDonald、Brian A Keay

  DOI：10.1139/v03-173

  日期：2004.2.1

  (±)-2,2′-Bis(diphenylphosphino)-3,3′-binaphtho[2,1-b]furan (BINAPFu) was synthesized from 2-naphthoxyacetic acid in a five-step sequence in 62% overall yield. A variety of reported resolution procedures for biaryl bisphosphines did not work with (±)-BINAPFu; thus, a new resolution method was developed, involving the Staudinger reaction of the aforementioned racemate of BINAPFu with an enantiopure camphor sulfonyl azide derivative. The resulting diastereomeric phosphinimines were separated by flash chromatography. Subsequent hydrolysis to the corresponding bis-phosphine oxide and trichlorosilane reduction provided enantiopure BINAPFu. The absolute stereochemical configuration of BINAPFu was established by X-ray crystallography. BINAPFu was compared with commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) in Pd(0)-catalyzed intermolecular Heck reactions. Investigation of the Heck arylation of 2,3-dihydrofuran showed BINAPFu to be more efficacious than BINAP in dioxane at 30 °C. A variety of phosphorus selenides were prepared, and the ¹J_P-Se coupling constants measured, to obtain a comparative scale of parent phosphine basicity. The phosphorus atoms in BINAPFu were found to be electron deficient when compared with BINAP but slightly more electron rich than trifurylphosphine. Key words: naphthofurans, atropisomers, electron-deficient phosphines, asymmetric Heck reactions, Staudinger reaction.

  (±)-2,2′-双(二苯基膦基)-3,3′-双萘[2,1-b]呋喃（BINAPFu）是从2-萘氧乙酸经过五步反应合成，总产率为62%。许多报道的对联双膦酯的分离方法对（±）-BINAPFu无效；因此，开发了一种新的分离方法，涉及BINAPFu的上述外消旋体与手性纯的樟脑磺酰叠氮化合物进行Staudinger反应。通过快速色谱法分离出产物的异构磷亚胺。随后的水解得到相应的双膦氧化物，经三氯硅烷还原得到手性纯的BINAPFu。通过X射线晶体学确定了BINAPFu的绝对立体化学构型。在Pd(0)催化的分子间Heck反应中，将BINAPFu与市售的2,2′-双(二苯基膦基)-1,1′-双萘烷（BINAP）进行比较。研究2,3-二氢呋喃的Heck芳基化反应表明，在30°C的二甲醚中，BINAPFu比BINAP更有效。制备了多种磷硒化合物，并测量了¹J_P-Se偶合常数，以获得父膦碱度的比较尺度。与BINAP相比，BINAPFu中的磷原子被发现是电子亏缺的，但比三呋烷基膦富含电子略多。关键词：萘呋喃、对映异构体、电子亏缺磷化合物、不对称Heck反应、Staudinger反应。
• Determination of enantiomeric purity of hydroxy biaryls using 1H and 31P-NMR on their diazaphospholidine derivatives
  作者：A. Alexakis、J.C. Frutos、P. Mangeney、A.I. Meyers、Henk Moorlag

  DOI：10.1016/s0040-4039(00)77044-4

  日期：1994.7

  Chiral biaryl alcohols were readily transformed in a single step, with chiral nonracemic 1,2-diamines, PCl3, and sulfur in CDCl3 - all in a NMR tube - to their diastereomeric diazaphospholidines and their diastereomeric ratios (also ee's) assessed directly.