(1S,2S)-1,2-trans-bis-(diphenylphosphinooxy)cyclohexane

• 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: (1S,2S)-1,2-trans-bis-(diphenylphosphinooxy)cyclohexane
• 英文别名: (1S,2S)-bis-diphenylphosphinoxycyclohexane；(1S,2S)-1,2-bis-O-(diphenylphosphino)cyclohexane；[(1S,2S)-2-diphenylphosphanyloxycyclohexyl]oxy-diphenylphosphane
• 化学式: C₃₀H₃₀O₂P₂
• 分子量: 484.515
• InChiKey: RBJWTUHNUVPCOR-KYJUHHDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺 在 吡啶 、 盐酸 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 18.75h， 生成 (1S,2S)-1,2-trans-bis-(diphenylphosphinooxy)cyclohexane
  参考文献：
  名称：

  Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of R- or S-Amino Acids Using Natural Sugars as Ligand Precursors

  摘要：

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.

  DOI：

  10.1021/jo970884d

文献信息

• Electronic Effects in Asymmetric Catalysis:  Structural Studies of Precatalysts and Intermediates in Rh-Catalyzed Hydrogenation of Dimethyl Itaconate and Acetamidocinnamic Acid Derivatives Using <i>C</i>₂-Symmetric Diarylphosphinite Ligands
  作者：T. V. RajanBabu、Branko Radetich、Kamfia K. You、Timothy A. Ayers、Albert L. Casalnuovo、Joseph C. Calabrese

  DOI：10.1021/jo9901182

  日期：1999.5.1

  largely unaffected by electronic effects, which suggests that other explanations have to be sought for the electronic amplification of enantioselectivity. One possibility is a change in the diastereomeric equilibrium between the initially formed [substrate]Rh(+)[phosphinite] complexes as a function of electronic effect of the ligand. In the Rh-catalyzed hydrogenation of dimethyl itaconate, we have examined

  的Rh（I）的对映选择性的催化的脱氢氨基酸衍生物的不对称氢化和衣康酸二甲酯可以通过对来自碳水化合物以及反式 - 环己烷-1,2-二醇衍生的邻位diarylphosphinites的芳香环的取代基的合适的选择来增强。例如，使用在磷处具有给电子双（3,5-二甲基苯基）基团的次膦酸盐在这些反应中提供了高ee，而吸电子芳基取代基降低了对映选择性。在本文中，我们试图从两个层面上阐明这些非凡的电子效应的起源。首先，确定了多种预催化剂（[亚膦酸酯]（2）Rh（+）[二烯烃] X（-））的晶体结构，并对其结构进行了详细研究，以检查电子效应（如果有），这些分子的基态构象。对其中六种配合物的研究表明，这些预催化剂的总体构象特征在很大程度上不受电子效应的影响，这表明对电子选择性的对映选择性必须寻求其他解释。一种可能是初始形成的[底物] Rh（+）[亚膦酸酯]配合物之间的非对映异构体平衡随配体电子效应的变化而变化
• Ruthenium complexes of chiral diphosphinite ligands with cyclohexane or <i>chiro</i> -inositol backbones as catalysts for asymmetric hydrogenation reactions
  作者：George R. Clark、Andrew Falshaw、Graeme J. Gainsford、Cornelis Lensink、Angela T. Slade、L. James Wright

  DOI：10.1080/00958970903502744

  日期：2010.2.10

  Treatment of [RuCl2(COD)] n with the chiral diphosphinite ligand (1S,2S)-1,2-trans-bis-(O-diphenylphosphino)cyclohexane [(1S,2S)-14] and triethylamine gives the bis(diphosphinite) complex RuHCl[(1S,2S)-14]2 (15) in good yield. If (rac)-1,2-trans-bis-(O-diphenylphosphino)cyclohexane [(rac)-14] is used in place of (1S,2S)-14 in this reaction, a racemic mixture of RuHCl[(1S,2S)-14]2 and RuHCl[(1R,2R)-14]2

  [RuCl2(COD)] n 用手性二亚膦酸配体 (1S,2S)-1,2-trans-bis-(O-diphenylphosphino)cyclohex [(1S,2S)-14] 和三乙胺处理得到双（二亚膦酸） ) 络合物 RuHCl[(1S,2S)-14]2 (15) 收率良好。如果在该反应中使用 (rac)-1,2-反式-双-(O-二苯基膦基)环​​己烷 [(rac)-14] 代替 (1S,2S)-14，则 RuHCl[(1S) 的外消旋混合物,2S)-14]2 和 RuHCl[(1R,2R)-14]2 [(rac)-16] 形成。(rac)-16·(2.5CH2Cl2)的X射线晶体结构已经确定。(rac)-16 在异丙醇中用氢气处理导致形成 RuH2[(1S,2S)-14]2 和 RuH2[(1R,2R)-14]2[(rac)-的外消旋混合物] 17]。(rac)-17 的结构由外消旋晶体的
• Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of <i>R</i>- or <i>S</i>-Amino Acids Using Natural Sugars as Ligand Precursors
  作者：T. V. RajanBabu、Timothy A. Ayers、Gary A. Halliday、Kimberly K. You、Joseph C. Calabrese

  DOI：10.1021/jo970884d

  日期：1997.8.1

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.