Sn(3,5-C6Cl2F3)Bu3 | 213135-39-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: Sn(3,5-C6Cl2F3)Bu3
• 英文别名: RfSnBu3
• CAS: 213135-39-8
• 化学式: C₁₈H₂₇Cl₂F₃Sn
• 分子量: 490.024
• InChiKey: WCMYQNCOSIVIPZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.98
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-氯丙烯 、 Sn(3,5-C6Cl2F3)Bu3 在 对苯醌 作用下， 以 氘代氯仿 为溶剂， 反应 1.0h， 以89%的产率得到1-Allyl-3,5-dichloro-2,4,6-trifluoro-benzene
  参考文献：
  名称：

  Pd催化的烯丙基卤与锡芳基的偶合：为什么催化反应有效而化学计量反应无效。

  摘要：

  芳基烯丙基铝配合物[Pd（5-C6F5-eta3-环己烯基）（C6Cl2F3）（NCMe）]（10）和[Pd2（mu-C6Cl2F3）2（5-C6F5-1,3-eta3-环己烯基）2]（13）已经合成。配合物13是具有芳基桥的稀有金属配合物的实例，并且已经确定了其X射线晶体衍射结构。这些芳基烯丙基铝络合物参与Bu3SnRf（1，Rf =二氯三氟苯基）和[Pd2（mu-Br）2（5-C6F5-1,3-eta3-环己烯基）2]（2）的偶联。在乙腈中的化学计量偶合反应过程中已检测到络合物10。在不同条件下进行10和13的分解实验，并与1和2的反应进行比较，我们可以确定在没有添加剂的情况下不会发生还原消除。对苯醌与Pd配位得到络合物15，并促进还原消除，从而选择性地产生偶联产物。偶联反应的结果受还原消除步骤的控制，但总速率受更快的预平衡控制，预平衡决定了10或13的浓度。钯催化的烯丙基卤化物和锡芳

  DOI：

  10.1002/1521-3765(20010601)7:11<2481::aid-chem24810>3.0.co;2-2
• 作为产物：
  描述：

  三丁基乙烯基锡 以 四氢呋喃 、 乙醚 为溶剂， 生成 Sn(3,5-C6Cl2F3)Bu3
  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。
• Quantitative Evaluation of the Factors Contributing to the “Copper Effect” in the Stille Reaction
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/om020896b

  日期：2003.3.1

  The relative importance of the factors contributing to the accelerating effect of CuI on [PdL4]-catalyzed couplings of (RI)-I-1 and (RSnBu3)-Sn-2 (copper effect) has been quantitatively evaluated in THF for R-1 = 3,5-C6Cl2F3; R-2 = vinyl, C6H4-4-OMe; L = AsPh3, PPh3, using spectroscopic and kinetic methods. The F-19 NMR kinetic data show that the rate enhancement produced by addition of CuI is strongly related with the "autoretardation" effect intrinsic to [PdL4] catalysts and is almost independent of the organotin reagent (vinyl, aryl). The "autoretardation" is due to the release of 2 equiv of L during the oxidation of [PdL4] to yield trans-[(PdRIL2)-I-1], which is the species undergoing transmetalation. CuI does not promote the dissociation of L from trans- [(PdRIL2)-I-1], but it captures part of the free neutral ligand L and therefore mitigates the autoretardation produced by the presence of free L on the rate-determining associative transmetalation. In the conditions studied (Pd:Cu = 1:2; T = 322.6 K; THF as solvent), for L = AsPh3 the CuI added captures about 25% of the free AsPh3 and the copper effect compensates only ca. 1% of the autoretardation, whereas for L = PPh3 the CuI captures about 99% of the free PPh3 and the compensation is about 30%. This remarkable variation is caused by the combined effect of two independent factors: W The catalyst [Pd-(PPh3)](4) is more autoretarded than [Pd(AsPh3)(4)]; and (ii) CuI is a more effective scavenger for PPh3 than for AsPh3.
• Problematic Ar^F–Alkynyl Coupling with Fluorinated Aryls. From Partial Success with Alkynyl Stannanes to Efficient Solutions via Mechanistic Understanding of the Hidden Complexity
  作者：Guillermo Marcos-Ayuso、Marconi N. Peñas-Defrutos、Ana M. Gallego、Max García-Melchor、Jesús M. Martínez-Ilarduya、Pablo Espinet

  DOI：10.1021/jacs.2c10842

  日期：2023.1.11
• Mechanism of the Stille Reaction. 2. Couplings of Aryl Triflates with Vinyltributyltin. Observation of Intermediates. A More Comprehensive Scheme
  作者：Arturo L. Casado、Pablo Espinet、Ana M. Gallego

  DOI：10.1021/ja001511o

  日期：2000.12.1

  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.
• The Pd-Catalyzed Coupling of Allyl Halides and Tin Aryls: Why the Catalytic Reaction Works and the Stoichiometric Reaction Does Not
  作者：Ana C. Albéniz、Pablo Espinet、Blanca Martín-Ruiz

  DOI：10.1002/1521-3765(20010601)7:11<2481::aid-chem24810>3.0.co;2-2

  日期：2001.6.1

  the course of the stoichiometric coupling reaction in acetonitrile. Decomposition experiments of 10 and 13 in different conditions, and comparison with the reactions of 1 and 2, allow us to determine that reductive elimination does not occur in the absence of additives. p-Benzoquinone coordinates to Pd to give complex 15 and promotes reductive elimination to give the coupling products selectively.

  芳基烯丙基铝配合物[Pd（5-C6F5-eta3-环己烯基）（C6Cl2F3）（NCMe）]（10）和[Pd2（mu-C6Cl2F3）2（5-C6F5-1,3-eta3-环己烯基）2]（13）已经合成。配合物13是具有芳基桥的稀有金属配合物的实例，并且已经确定了其X射线晶体衍射结构。这些芳基烯丙基铝络合物参与Bu3SnRf（1，Rf =二氯三氟苯基）和[Pd2（mu-Br）2（5-C6F5-1,3-eta3-环己烯基）2]（2）的偶联。在乙腈中的化学计量偶合反应过程中已检测到络合物10。在不同条件下进行10和13的分解实验，并与1和2的反应进行比较，我们可以确定在没有添加剂的情况下不会发生还原消除。对苯醌与Pd配位得到络合物15，并促进还原消除，从而选择性地产生偶联产物。偶联反应的结果受还原消除步骤的控制，但总速率受更快的预平衡控制，预平衡决定了10或13的浓度。钯催化的烯丙基卤化物和锡芳