[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)] | 827336-47-0

• 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: [(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)]
• 英文别名: δ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)]；λ-[(Me4-NUPHOS)Pt((S)-BINOL)]；λ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)Pt((S)-BINOL)]；δ-[(Me4-NUPHOS)Pt((S)-BINOL)]
• CAS: 827336-47-0；622853-41-2；827336-97-0
• 化学式: C₅₂H₄₄O₂P₂Pt
• 分子量: 957.948
• InChiKey: DFHUXKZZPCTWSY-ZENHEBGASA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)] 以 甲苯 为溶剂， 生成 λ-[(1,4-bis(diphenylphosphino)-1,2,3,4-tetramethyl-1,3-butadiene)platinum((S)-BINOL)]
  参考文献：
  名称：

  Comparative Study of Diastereoisomer Interconversion in Chiral BINOL-ate and Diamine Platinum Complexes of Conformationally Flexible NUPHOS Diphosphines

  摘要：

  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.

  DOI：

  10.1021/om034289f

文献信息

• 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％。
• 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.