(S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-[bis(3,5-di-tert-butylphenyl)phosphino]-1,1'-binaphthyl

• 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: (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-[bis(3,5-di-tert-butylphenyl)phosphino]-1,1'-binaphthyl
• 英文别名: bis(3,5-ditert-butylphenyl)-[1-[2-[(4S)-4-propan-2-yl-4,5-dihydro-1,3-oxazol-2-yl]naphthalen-1-yl]naphthalen-2-yl]phosphane
• 化学式: C₅₄H₆₄NOP
• 分子量: 774.082
• InChiKey: ALAUOQCRYPSFOA-YACUFSJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.3
• 重原子数：
  57
• 可旋转键数：
  10
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-[bis(3,5-di-tert-butylphenyl)phosphino]-1,1'-binaphthyl 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 以 四氢呋喃 为溶剂， 以62%的产率得到Pd(dba)((S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-[bis(3,5-di-tert-butylphenyl)phosphino]-1,1'-binaphthyl)
  参考文献：
  名称：

  Dialkyl Effect on Enantioselectivity:  π-Stacking as a Structural Feature in P,N Complexes of Palladium(II)

  摘要：

  A phosphino,oxazoline P,N-bidentate ligand, 4, containing 3,5-di-tert-butylphenyl groups has been prepared. In the Heck arylation of dihydrofuran, 4 is shown to afford higher ee's than either 2 or 3, the unsubstituted and m-dimethylphenyl analogues, respectively. Several Pd(0) complexes of 4 are reported. The exchange dynamics of Pd(4)(dba) are shown to involve an interconversion of diastereomers via an intramolecular process. The X-ray structure for PdCl2(4), 8, was determined by X-ray diffraction methods. Comparison of data with PdCl2(2), 9, and PdCl2(3), 10, suggests that differing amounts of stacking influence the structures of these relatively simple Pd complexes, with 9 and 10 revealing the strongest, pi-pi interactions. An estimation of the van der Waals energies involved in the interaction supports a ca. 4 kcal/mol stabilization via pi-pi stacking.

  DOI：

  10.1021/om020314q

文献信息

• 3,5-Dialkyl Effect on Enantioselectivity in Pd Chemistry:  Applications Involving Both Bidentate and Monodentate Auxiliaries
  作者：Pascal Dotta、P. G. Anil Kumar、Paul S. Pregosin、Alberto Albinati、Silvia Rizzato

  DOI：10.1021/om034381b

  日期：2004.5.1

  The structural 3,5-dialkylphenyl effect on enantioselectivity is demonstrated for several Pd-catalyzed reactions including a ring-opening transmetalation, Heck arylation, and allylic alkylation. For these homogeneously catalyzed reactions the observed enantiomeric excesses (ee's) are found to improve by more than 15%. The ligands tested include MeO-Biphep and a P,N-phosphino-oxazoline-bidentate ligand containing 3,5-di-tert-butylphenyl substituents. Further, several derivatives of the monodentate auxiliary MOP ((R)-2-diarylphosphino-1,1'-binaphthyl) have been modified to include 3,5-dialkylphenyl substituents and these auxiliaries have been tested in Pd-catalyzed enantioselective hydrosilylation chemistry. For some, but not all of these MOP ligands, enhanced ee's of the order of 40-50% are found. Variable-temperature and 2-D NMR studies have been carried out on new model complexes and reveal selected restricted rotation around a number of the P-C(Ipso) aryl bonds. Solid-state structures for two of the new complexes, PdBr(p-NCC6H4)(phosphino-oxazoline, 2b), 8b, and PdCl(C6H4CH2NMe2)(MOP, 4b), 9b, have been determined.
• Dialkyl Effect on Enantioselectivity:  π-Stacking as a Structural Feature in P,N Complexes of Palladium(II)
  作者：Pascal Dotta、Alessandra Magistrato、Ursula Rothlisberger、Paul S. Pregosin、Alberto Albinati

  DOI：10.1021/om020314q

  日期：2002.7.1

  A phosphino,oxazoline P,N-bidentate ligand, 4, containing 3,5-di-tert-butylphenyl groups has been prepared. In the Heck arylation of dihydrofuran, 4 is shown to afford higher ee's than either 2 or 3, the unsubstituted and m-dimethylphenyl analogues, respectively. Several Pd(0) complexes of 4 are reported. The exchange dynamics of Pd(4)(dba) are shown to involve an interconversion of diastereomers via an intramolecular process. The X-ray structure for PdCl2(4), 8, was determined by X-ray diffraction methods. Comparison of data with PdCl2(2), 9, and PdCl2(3), 10, suggests that differing amounts of stacking influence the structures of these relatively simple Pd complexes, with 9 and 10 revealing the strongest, pi-pi interactions. An estimation of the van der Waals energies involved in the interaction supports a ca. 4 kcal/mol stabilization via pi-pi stacking.