(S)-BINAP(S) | 669091-51-4

• 英文名称: (S)-BINAP(S)
• 英文别名: [1-(2-diphenylphosphanylnaphthalen-1-yl)naphthalen-2-yl]-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 669091-51-4
• 化学式: C₄₄H₃₂P₂S
• 分子量: 654.752
• InChiKey: XQECHJKMCCHAKF-UHFFFAOYSA-N

物化性质

• 沸点：
  770.1±70.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.6
• 重原子数：
  47
• 可旋转键数：
  7
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  sodium hexafluoroantimonate 、 bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)] 、 (S)-BINAP(S) 以 二氯甲烷 为溶剂， 以82%的产率得到[(η3-1-phenylallyl)Pd(S-BINAP(S))]SbF6
  参考文献：
  名称：

  Regioselectivity in the Palladium/(S)-BINAP(S)-Catalyzed Asymmetric Allylic Amination:  Reaction Scope, Kinetics, and Stereodynamics

  摘要：

  Studies defining the scope of the reaction and understanding the factors controlling the unusual regioselectivity observed in the Pd/{BINAP(S)}-catalyzed allylic amination reaction are presented. Most of the unsymmetrically substituted allylic substrates tested show regioselectivity that is the reverse of that which would normally be expected in Pd-catalyzed systems. Several cationic eta(3)-allylic complexes containing a Pd{BINAP(S)} fragment have been synthesized in an attempt to correlate this behavior with structural features of the ligand and the solution structure of the allylpalladium complex. Notably, allylic amines with an alpha-quaternary carbon center may be prepared with high regioselectivity with this system. Spin-saturation transfer studies (SST) were performed on two (kappa(2)-P,S)Pd-pi-allyl complexes in order to determine relative rates for Pd-eta(3)-eta(1)-eta(3)-allyl interconversions and the hemilabile behavior of the BINAP(S) ligand.

  DOI：

  10.1021/om050537r
• 作为产物：
  描述：

  (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 在 sulfur 作用下， 以 苯 为溶剂， 反应 2.5h， 以37%的产率得到(S)-BINAP(S)
  参考文献：
  名称：

  Diphosphine mono-sulfides: readily available chiral monophosphines

  摘要：

  Enantiomerically pure (R)-BINAP, (R)-Tol-BINAP, (R,R)-Me-DUPHOS and (R,R)-DIOP were converted into the corresponding mono-sulfides by treatment with elemental sulfur in benzene. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00088-0

文献信息

• Regioselectivity and memory effects in palladium catalyzed allylic alkylations with bidentate P^PS donor ligands
  作者：Suzanna C. Milheiro、J.W. Faller

  DOI：10.1016/j.jorganchem.2010.10.022

  日期：2011.2

  bidentate bisphosphine monosulfide ligands, were found to catalyze allylic alkylation reactions with high branched:linear selectivity with some ligands. Some of these catalysts also display a regiochemical memory effect, in which the hemilability and rigidity of the P^PS ligands affect the reaction rate and the degree to which a memory effect is observed.

  一系列配合物，[将Pd（η 3 -C 3 H ^ 5）（P ^ P小号）] [的SbF 6 ]，其中P ^ P小号是二齿膦配位体一硫化物，发现催化具有高支化烯丙基烷基化反应：有一些配体的线性选择性。这些催化剂也显示区域化学记忆效应，其中，所述的hemilability和刚性P ^ P小号配体影响反应速率和被观察到的记忆效应的程度。
• Hemilability and nonrigidity in metal complexes of bidentate P,PS donor ligands
  作者：J.W. Faller、Suzanna C. Milheiro、Jonathan Parr

  DOI：10.1016/j.jorganchem.2007.10.044

  日期：2008.4

  Hemilability and nonrigidity in a series of mixed P, P=S donor ligands has been studied in the complexes [Pd(P, P=S)Cl(2)], [Pd(eta(3)-C(3)H(5)) (P, P=S)][SbF(6)], and [Rh(cod)(P, P=S)][SbF(6)] (P, P=S = Ph(2)P-Q-P(S)Ph(2)). The effect of bite angle, the rigidity of the ligand backbone, and the role of the ancillary ligands are discussed. (C) 2007 Elsevier B.V. All rights reserved.