trans-[Pd(C6F5)(OTf)(AsPh3)2] | 321601-61-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: trans-[Pd(C6F5)(OTf)(AsPh3)2]
• CAS: 321601-61-0
• 化学式: C₄₃H₃₀As₂F₈O₃PdS
• 分子量: 1035.03
• InChiKey: LTYCGZMWVSIZAJ-UHFFFAOYSA-M

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：
  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(C6F5)(OTf)(AsPh3)2] 、 三丁基乙烯基锡 以 氯苯 为溶剂， 生成 三正丁基锡三氟基磺酸盐
  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：

  [Pd(μ-Cl)(C6F5)(tetrahydrothiophene)]2 、 三苯胂 以 二氯甲烷 、 丙酮 为溶剂， 生成 trans-[Pd(C6F5)(OTf)(AsPh3)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