trans-[Pd(3,5-C6Cl2F3)(OTf)(PPh3)2] | 321601-62-1

• 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: trans-[Pd(3,5-C6Cl2F3)(OTf)(PPh3)2]
• 英文别名: trans-[Pd(PPh3)2(2,4,6-trifluoro-3,5-dichlorophenyl)(OTf)]
• CAS: 321601-62-1
• 化学式: C₄₃H₃₀Cl₂F₆O₃P₂PdS
• 分子量: 980.039
• InChiKey: LBYUSEJPKIMBCO-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：

  trans-[Pd(3,5-C6Cl2F3)(OTf)(PPh3)2] 以 四氢呋喃 、 甲苯 为溶剂， 生成 [Pd(3,5-C6Cl2F3)(N-methyl-2-pyrrolidinone)(PPh3)2]BF4
  参考文献：
  名称：

  Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme

  摘要：

  The mechanism of the [PdL4]-catalyzed couplings between R-OTf (R = pentahalophenyl; L = PPh3, AsPh3) and Sn(CH=CH2)Bu-3 has been studied. The addition of LiCl favors the coupling for L = AsPh3 in THF but retards it for L = PPh3. Separate experiments show that for L = AsPhs, LiCl accelerates the otherwise very slow and rate-determining oxidative addition of the aryl triflate to [PdL4], leading to trans[PdRClL2]. Therefore, the overall process is accelerated. For L = PPh3, the rate-determining step is the transmetalation. Complex trans-[PdRXL2],with X = Cl, is formed in the presence of LiCl, whereas an equilibrium mixture mainly involving species with X = TfO, L, or S (S = solvent) is established in the absence of LiCl. Since the transmetalation is slower for X = Cl than for the other complexes, the overall process is retarded by addition of LiCl. The transmetalation in complexes trans-[PdRXL2], with X = Cl, follows the S(E)2(cyclic) mechanism proposed in Part 1 (Casado, A. L.; Espinet, P. J. Am. Chem. Sec. 1998, 120, 8978-8985), giving the coupling product R-CH=CH2 directly. For X = TfO or, L rather stable intermediates trans[PdR(CH=CH2)L-2] are detected, Supporting an SE2(open) mechanism. The I;ey:intermediates undergoing transmetalation in the conditions arid solvents most commonly used in the literature have been identified.;The operation of S(E)2(cyclic) and S(E)2(open) pathways emphasizes common aspects of the Stille reaction with the Hiyama reaction where, using (RSiF3)-Si-2 that is chiral at the alpha -carbon of R retention or inversion gt the transmetalated chiral carbon can be-induced. This helps us to understand the contradictory stereochemical outcomes in the literature for Stille couplings using (RSnR3)-Sn-2 derivatives that are chiral Bt the a-carbon of R-2 and suggests that stereocontrol of the Stille reaction might be achieved.

  DOI：

  10.1021/ja001511o
• 作为产物：
  描述：

  trans-[Pd(3,5-dichlorotrifluorophenyl)Cl(PPh3)2] 、 silver trifluoromethanesulfonate 以 二氯甲烷 、 丙酮 为溶剂， 以60%的产率得到trans-[Pd(3,5-C6Cl2F3)(OTf)(PPh3)2]
  参考文献：
  名称：

  Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme

  摘要：

  The mechanism of the [PdL4]-catalyzed couplings between R-OTf (R = pentahalophenyl; L = PPh3, AsPh3) and Sn(CH=CH2)Bu-3 has been studied. The addition of LiCl favors the coupling for L = AsPh3 in THF but retards it for L = PPh3. Separate experiments show that for L = AsPhs, LiCl accelerates the otherwise very slow and rate-determining oxidative addition of the aryl triflate to [PdL4], leading to trans[PdRClL2]. Therefore, the overall process is accelerated. For L = PPh3, the rate-determining step is the transmetalation. Complex trans-[PdRXL2],with X = Cl, is formed in the presence of LiCl, whereas an equilibrium mixture mainly involving species with X = TfO, L, or S (S = solvent) is established in the absence of LiCl. Since the transmetalation is slower for X = Cl than for the other complexes, the overall process is retarded by addition of LiCl. The transmetalation in complexes trans-[PdRXL2], with X = Cl, follows the S(E)2(cyclic) mechanism proposed in Part 1 (Casado, A. L.; Espinet, P. J. Am. Chem. Sec. 1998, 120, 8978-8985), giving the coupling product R-CH=CH2 directly. For X = TfO or, L rather stable intermediates trans[PdR(CH=CH2)L-2] are detected, Supporting an SE2(open) mechanism. The I;ey:intermediates undergoing transmetalation in the conditions arid solvents most commonly used in the literature have been identified.;The operation of S(E)2(cyclic) and S(E)2(open) pathways emphasizes common aspects of the Stille reaction with the Hiyama reaction where, using (RSiF3)-Si-2 that is chiral at the alpha -carbon of R retention or inversion gt the transmetalated chiral carbon can be-induced. This helps us to understand the contradictory stereochemical outcomes in the literature for Stille couplings using (RSnR3)-Sn-2 derivatives that are chiral Bt the a-carbon of R-2 and suggests that stereocontrol of the Stille reaction might be achieved.

  DOI：

  10.1021/ja001511o

文献信息

• Stille Coupling of Alkynyl Stannane and Aryl Iodide, a Many-Pathways Reaction: The Importance of Isomerization
  作者：Mónica H. Pérez-Temprano、Ana M. Gallego、Juan A. Casares、Pablo Espinet

  DOI：10.1021/om100978w

  日期：2011.2.14

  The kinetics of the Stille reaction between C6Cl2F3I and PhCCSnBu3 have been studied for the whole catalytic system and for transmetalations as separate steps. The use of (trifluorodichlorophenyl)palladium derivatives slows down the reactions and allows for the observation of the intermediates cis- and trans-[Pd(C6Cl2F3)I(PPh3)2]. The first is formed in the oxidative addition step and isomerizes to

  C 6 Cl 2 F 3 I和PhCCSnBu 3之间的Stille反应动力学已针对整个催化系统和作为单独步骤的重金属化进行了研究。（三氟二氯苯基）钯衍生物的使用减慢了反应的速度，并允许观察到中间体顺式和反式[Pd（C 6 Cl 2 F 3）I（PPh 3）2]。第一个在氧化加成步骤中形成并异构化为第二个。两者均被研究为整个循环的催化剂。动力学研究比较了每种异构体的重金属化步骤的相关性。竞争的金属转移物同时产生顺式和反式-[Pd（C 6 Cl 2 F 3）（PhCC）（PPh 3）2 ]。前者经历了非常快的C-C耦合，而第二者由于极慢的异构化而积累在溶液中。因此，该系统是对Stille反应中竞争途径的影响及其对催化过程性能的影响的案例研究。