PdBr(4-cyanophenyl)(TMEDA) | 264151-60-2

• 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: PdBr(4-cyanophenyl)(TMEDA)
• 英文别名: Pd(N,N,N',N'-tetramethylethylenediamine)(4-cyanophenyl)Br；[PdBr(p-CN-C6H4)(TMEDA)]；benzonitrile;bromopalladium(1+);N,N,N',N'-tetramethylethane-1,2-diamine
• CAS: 264151-60-2
• 化学式: C₁₃H₂₀BrN₃Pd
• 分子量: 404.646
• InChiKey: GIIMQUXABMAIDL-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  (R)-(+)-(6,6′-二甲氧联苯-2,2′-二基)双(二苯基膦) 、 PdBr(4-cyanophenyl)(TMEDA) 以 四氢呋喃 为溶剂， 以69%的产率得到PdBr(p-NCC6H4)((S)-((C6H3(OCH3)P(C6H5)2)2))
  参考文献：
  名称：

  使用MeO-Biphep配体对对映选择性Heck反应的贡献。反对二亚苄基丙酮的案子

  摘要：

  结果表明，当螯合二膦MeO-Biphep 1a被其二取代取代时，p -XC 6 H 4 OTf，X = OMe，H，CO 2 Me与Pd催化的Pd对映选择性Heck反应具有更高的对映选择性。类似物3,5-二叔丁基MeO-Biphep，1b。5-甲基-2,3-二氢呋喃的苯基化可产生一种新的二氢呋喃，其中含有一个四级立体异构中心（ee，> 98％，1b，大约20％，1a）。三氟甲磺酸苯酯与dhf反应的催化结果，以及芳基卤化物在Pd配合物为1时的化学计量氧化加成反应的结果表明，相对于由PdCl 2（1）+ NaBH 4生成Pd（0）前体的反应，使用Pd（dba）（1）dba =二亚苄基丙酮会减慢氧化加成反应。报告了两种PdI（芳基）（1a）3衍生物的固态结构，芳基= p -MeOOC-C 6 H 4（3a）和C 6 F 5（3b）。

  DOI：

  10.1021/om980783l

文献信息

• Catalytic and Structural Studies on Complexes of a Binaphthyl−Phosphino−Oxazoline Auxiliary:  The Meta Dialkyl Effect on Enantioselectivity
  作者：Kumaravel Selvakumar、Massimiliano Valentini、Paul S. Pregosin、Alberto Albinati、Frank Eisenträger

  DOI：10.1021/om990892f

  日期：2000.4.1

  The chiral phosphino-oxazoline ligand (S,R)-2-[4-(isopropyl)oxazol-2-yl]-2'-bis(3,5-dimethylphenylphosphino)-1,1'-binaphthyl, 6b, its Pd-dichloro complex, 9, the p-cyanoaryl complex [PdBr(p-NC-C6H4](6b)], 10, a model for the Heck reaction, the cationic 1,3-diphenylallyl derivative [Pd(eta(3)-PhCHCHCHPh)(6b)]OTf, 11, a model for the allylic allylation, and the Rh- and Ir-1,5-COD compounds [M(1,5-COD)(6b)]BF4, 12 and 13, respectively, have been prepared. In enantioselective catalytic experiments, the presence of the 3,5-dimethylphenyl groups generally increases the observed ee. The solid-state structure of PdCl2(6b), 9, has been determined. 2-D and variable-temperature NMR experiments suggest that one of the two 3,5-dimethyl P-aryl rings interacts selectively with the remaining ligands. Consequently, the entire chiral pocket becomes slightly more rigid and the correlation with substrate improves.
• Palladium−Duphos Structural and Enantioselective Hydroarylation Chemistry
  作者：Daniela Drago、Paul S. Pregosin

  DOI：10.1021/om0108898

  日期：2002.3.1

  A series of Pd(II) complexes of 1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene (MeDuphos; 1) have been prepared, and the solid-state structures for five of these, PdBr(p-CN-C6H4)(1), PdX(C6F5)(1) (X = Br, I), Pd(OAc)(2)(1), and [Pd(CH3CN)(2)(1)](PF6), have been determined by X-ray diffraction. Several of these complexes are catalyst precursors for the enantioselective hydroarylation of norbornene with PhX (X = Br, I, OTf). The maximum ee, 75%, is higher than the corresponding values previously reported for bidentate phosphine auxiliaries. NOESY NMR results show how complexed 1 interacts with the aryl ligand in PdBr(p-CN-C6H4)(1).
• 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.