δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)PtCl2] | 622853-55-8

• 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: δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)PtCl2]
• 英文别名: δ-[(Me4-NUPHOS)PtCl2]；λ-[(Me4-NUPHOS)PtCl2]；λ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)PtCl2]；λ-[(1,2,3,4-Me4-NUPHOS)PtCl2]；dichloroplatinum;[(2Z,4Z)-5-diphenylphosphanyl-3,4-dimethylhexa-2,4-dien-2-yl]-diphenylphosphane
• CAS: 622853-55-8；1000811-23-3
• 化学式: C₃₂H₃₂Cl₂P₂Pt
• 分子量: 744.54
• InChiKey: JQEOUVIVIVDXGH-BTWOGAGQSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  9.22
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)PtCl2] 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 生成 δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)Pt(OTf)2]
  参考文献：
  名称：

  Lewis Acid Platinum Complexes of Conformationally Flexible NUPHOS Diphosphines:  Highly Efficient Catalysts for the Carbonyl−Ene Reaction

  摘要：

  Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.

  DOI：

  10.1021/om0505716
• 作为产物：
  描述：

  盐酸 、 [(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)] 以 not given 为溶剂， 生成 δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)PtCl2]
  参考文献：
  名称：

  构型柔性NUPHOS型二膦的Lewis酸铂配合物催化的羰基化合物的高效不对称杂Diels-Alder反应

  摘要：

  构型上灵活的NUPHOS型二膦化合物已解析为非对映纯的BINOLate铂双酚酸酯络合物δ-和λ-[[NUPHOS）Pt {（S）-BINOL}]和相应的对映纯路易斯酸δ-和λ-[（NUPHOS）Pt（ OTf）2 ]是通过三氟甲磺酸质子化反应生成的，可作为非活化共轭二烯与芳基乙二醛和乙醛酸酯的异狄尔斯-阿尔德反应的高效催化剂，ee高达99％。

  DOI：

  10.1021/om049392z

文献信息

• Efficient Asymmetric Carbonyl-Ene Reactions Catalyzed by Platinum Metal Lewis Acid Complexes of Conformationally Flexible NUPHOS Diphosphines:  A Comparison with BINAP
  作者：Simon Doherty、Julian G. Knight、Catherine H. Smyth、Ross W. Harrington、William Clegg

  DOI：10.1021/om700954s

  日期：2007.12.1

  presence of a single diastereoisomer after addition of (S,S)-DPEN to the reaction mixture. The absolute and relative stereochemistry of a number of the ene products has been determined by single-crystal X-ray crystallography. The sense of asymmetric induction, the regioselectivity, and the exo diastereoselectivity are consistent with a stereochemical model based on a square-planar catalyst·pyruvate

  对路易斯酸催化的一系列单取代，不对称的1,1-二取代和三取代的烯烃与三氟丙酮酸乙酯的羰基-烯反应的比较研究表明，对映纯构象的对位NUPHOS二膦的铂络合物与对映异构体对映纯BINAP相当或优于它们。 。这些NUPHOS二膦的立体化学完整性在较长的时间内保持完好无损，这通过高ee值证明，即对于未反应的底物，需要> 20 h才能达到良好的转化率，并且添加（S，S后，存在单个非对映异构体，这是高ee值所证明的。）-DPEN加入反应混合物中。已经通过单晶X射线晶体学确定了许多烯产物的绝对和相对立体化学。不对称诱导，区域选择性，和感外非对映选择性是基于一个正方形平面催化剂·丙酮酸加合物的立体化学模型一致。使用基于Pd 2（dba）3和NUPHOS二膦的催化剂混合物，通过相应的芳族溴化物和烯丙基溴化镁之间的钯催化交叉偶联，可以方便地制备该研究所需的烯丙基苯衍生物。
• Highly Efficient Asymmetric Hetero-Diels−Alder Reactions of Carbonyl Compounds Catalyzed by Lewis Acid Platinum Complexes of Conformationally Flexible NUPHOS-Type Diphosphines
  作者：Simon Doherty、Julian G. Knight、Christopher Hardacre、He−Kuan Lou、Colin R. Newman、Rakesh K. Rath、Sarah Campbell、Mark Nieuwenhuyzen

  DOI：10.1021/om049392z

  日期：2004.12.1

  NUPHOS-type diphosphines have been resolved as their diastereopure platinum BINOLate complexes δ- and λ-[(NUPHOS)Pt(S)-BINOL}] and the corresponding enantiopure Lewis acids δ- and λ-[(NUPHOS)Pt(OTf)2], being generated by protonation with trifluoromethanesulfonic acid, act as highly efficient catalysts for the hetero-Diels−Alder reaction of nonactivated conjugated dienes with aryl glyoxals and glyoxylate

  构型上灵活的NUPHOS型二膦化合物已解析为非对映纯的BINOLate铂双酚酸酯络合物δ-和λ-[[NUPHOS）Pt （S）-BINOL}]和相应的对映纯路易斯酸δ-和λ-[（NUPHOS）Pt（ OTf）2 ]是通过三氟甲磺酸质子化反应生成的，可作为非活化共轭二烯与芳基乙二醛和乙醛酸酯的异狄尔斯-阿尔德反应的高效催化剂，ee高达99％。
• Comparative Study of Diastereoisomer Interconversion in Chiral BINOL-ate and Diamine Platinum Complexes of Conformationally Flexible NUPHOS Diphosphines
  作者：Simon Doherty、Colin R. Newman、Rakesh K. Rath、Jan-Albert van den Berg、Christopher Hardacre、Mark Nieuwenhuyzen、Julian G. Knight

  DOI：10.1021/om034289f

  日期：2004.3.1

  A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.
• Lewis Acid Platinum Complexes of Conformationally Flexible NUPHOS Diphosphines:  Highly Efficient Catalysts for the Carbonyl−Ene Reaction
  作者：Simon Doherty、Peter Goodrich、Christopher Hardacre、He−Kuan Luo、Mark Nieuwenhuyzen、Rakesh K. Rath

  DOI：10.1021/om0505716

  日期：2005.11.1

  Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.