bis(tri-tert-butylphosphine)palladium | 52359-16-7

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: bis(tri-tert-butylphosphine)palladium
• 英文别名: (i-Pr₃P)₂Pd；Pd(P(i-Pr)3)2；Palladium--tri(propan-2-yl)phosphane (1/2)；palladium;tri(propan-2-yl)phosphane
• CAS: 52359-16-7
• 化学式: C₁₈H₄₂P₂Pd
• 分子量: 426.899
• InChiKey: NFUIQPSPUZQLSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.38
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(tri-tert-butylphosphine)palladium 在 乙炔 作用下， 以 not given 为溶剂， 生成 Acetylene;palladium;tri(propan-2-yl)phosphane
  参考文献：
  名称：

  A Palladium-Catalyzed Stannole Synthesis

  摘要：

  A palladium-catalyzed (2 + 2 + 1) cycloaddition reaction of two C2H2 and one SnR(2) to form C-unsubstituted stannoles (C4H4)SnR(2) [R = CH(SiMe(3))(2) 2a, R(2) = {C(SiMe(3))(2)CH2}(2) 2c] is described. Catalysts are (R'(2)PC(2)H(4)PR'(2))Pd complexes (slow reaction) and (R'P-3)(2)Pd complexes (fast reaction). The mechanism of the catalysis has been elucidated in detail from stoichiometric reactions based on R = CH(SiMe(3))(2). For the [(R'(2)PC(2)H(4)PR'(2))Pd]-catalyzed system, the starting Pd(0)-ethene complexes (R'(2)PC(2)H(4)PR'(2))Pd(C2H4) (R' = Pr-i (3),(t)Bu (4)) react both with ethyne to give the Pd(0)-ethyne derivatives (R'(2)PC(2)H(4)PR'(2))Pd(C2H2) (R' = Pr-i (5), (t)Bu (6)) and with SnR(2) to yield the Pd(0)-Sn(II) adducts (R'(2)PC(2)H(4)PR'(2))Pd=SnR(2) (R' = Pr-i (7), (t)Bu (8)). The Pd-Sn bond [2.481(2) Angstrom] of 7 is very short, indicative of partial multiple bonding. Subsequent reactions of the Pd(0)-ethyne complexes 5 and 6 with SnR(2) or of the Pd(0)-Sn(II) complexes 7 and 8 with ethyne afford the 1,2-palladastannete complexes (R'2PC2H4-PR'(2))Pd(CH=CH)SnR(2) (Pd-Sn) (R' = Pr-i (10), (t)Bu (11)). The derivative with R' = Me (9) has also been synthesized. In 10 a Pd-Sn single bond [2.670(1) Angstrom] is present. Complexes 10 and 11 (as well as 7 and 8 but not 9) react slowly with additional ethyne at 20 degrees C to reform the Pd(0)-ethyne complexes 5 and 6 with concomitant generation of the stannole (C4H4)SnR(2) (2a). Likely intermediates of this reaction are the Pd(0)-eta(2)-stannole complexes (R'(2)PC(2)H(4)PR'(2))Pd(eta(2)-C(4)H(4)SnR(2)) (R' = Pr-i (12), (t)Bu (13)), which have been synthesized independently. The stannole ligand in 12, 13 is easily displaced by ethyne to yield 5 or 6 or by SnR(2) to yield 7 or 8. Thus, the isolated complexes 5-8 and 10-13 are conceivable intermediates of the catalytic stannole formation, and from their stoichiometric reactions the catalysis cycle can be assembled. For the [(R'P-3)(2)Pd]-catayyze system, the corresponding intermediates (Me(3)P)(2)Pd(C2H2) (15), ((Pr3P)-Pr-i)(2)Pd(C2H2) (17), (Me(3)P)(2)Pd=SnR(2) (18), ((Pr3P)-Pr-i)(2)Pd=SnR(2) (20), and (Me(3)P)(2)Pd(CH=CH)SnR(2) (Pd-Sn) (19) have been isolated or detected by NMR, and ((Pr3P)-Pr-i)(2)Pd(CH=CH)SnR(2) (Pd-Sn) (21) is postulated as an intermediate. The [(Me(3)P)(2)Pd] system (stannole formation above 0 degrees C) is catalytically more active than any of the [(R'(2)PC(2)H(4)PR'(2))Pd] systems (slow stannole formation for R' = (t)Bu at 20 degrees C). Most active is the [((Pr3P)-Pr-i)(2)Pd] system, allowing a catalytic synthesis of the stannole 2a from SnR(2) and ethyne at -30 degrees C [1% of 17; yield 2a: 87%; TON (turnover number): 87].By carrying out the catalysis in pentane at 20 degrees C (0.04% of 17), the TON is increased to 1074 but the yield of 2a is diminished to 43% due to uncatalyzed thermal side reactions.

  DOI：

  10.1021/ja952495b
• 作为产物：
  描述：

  四氟硼酸三异丙基膦 在 sodium hydride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 7.0h， 生成 bis(tri-tert-butylphosphine)palladium
  参考文献：
  名称：

  Suzuki-Miyaura 反应中难以捉摸的芳基钯 (II) 硼酸盐配合物的结构、动力学和计算表征

  摘要：

  在 Suzuki-Miyaura 交叉偶联反应中已经确定了经常调用的中间体的存在，其中包含关键的 Pd-OB 亚基，即“缺失的环节”。低温快速注入核磁共振波谱 (RI-NMR)、动力学研究和计算分析的使用使这些高度难以捉摸的物种的产生、观察和表征成为可能。确认含 Pd-OB 物种的中间体的能力提供了机会，以阐明在关键的金属转移步骤中有机部分从硼转移到钯的机制方面。具体而言，这些研究确定了两种不同的含有 Pd-OB 键的中间体，一种三配位 (6-B-3) 硼酸复合物和一种四配位 (8-B-4) 硼酸酯复合物，两者都进行金属转移，产生交叉偶联产物。对于这些配合物的化学计量反应，已经阐明了两种不同的机制途径：（1）通过未活化的 6-B-3 中间体进行金属转移，在过量配体存在下占主导地位，以及（2）通过活化的 8-B-进行金属转移4 中间体，缺乏配体。

  DOI：

  10.1021/jacs.6b13384
• 作为试剂：
  描述：

  2-氯喹啉 、 (3S,4R)-3-氨基-4-氟哌啶-1-甲酸叔丁酯 在 potassium phosphate 、 bis(tri-tert-butylphosphine)palladium 作用下， 反应 20.0h， 生成 tert-butyl (3S,4R)-4-fluoro-3-(quinolin-2-ylamino)piperidine-1-carboxylate
  参考文献：
  名称：

  [EN] 4-FLUOROPIPERIDINE OREXIN RECEPTOR ANTAGONISTS
  [FR] ANTAGONISTES DES RÉCEPTEURS DE L'OREXINE DE TYPE COMPOSÉS DE 4-FLUOROPIPÉRIDINE

  摘要：

  本发明涉及4-氟哌啶化合物，它们是促进睡眠的受体拮抗剂，可用于治疗或预防涉及促进睡眠的神经和精神障碍和疾病。该发明还涉及包含这些化合物的药物组合物，以及在预防或治疗涉及促进睡眠的这类疾病中使用这些化合物和组合物。

  公开号：

  WO2014113303A1

文献信息

• 1,6-Diene Complexes of Palladium(0) and Platinum(0):  Highly Reactive Sources for the Naked Metals and [L−M⁰] Fragments
  作者：Jochen Krause、Günter Cestaric、Karl-Josef Haack、Klaus Seevogel、Werner Storm、Klaus-Richard Pörschke

  DOI：10.1021/ja983939h

  日期：1999.10.1

  1−12 react with donor ligands such as phosphanes, phosphites, or tBuNC to give isolated complexes of types L−M(1,6-diene) (13−41), which have also been prepared by other routes. In all complexes the metal centers are TP-3 coordinated: complexes 1−4 contain chelating and bridging 1,6-diene ligands, whereas the other complexes contain a chelating 1,6-diene ligand and an η2-a...

  配合物 (cod)MCl2 (M = Pd, Pt; cod = cis,cis-1,5-cyclooctadiene) 与 Li2(cot) (cot = cyclooctatetraene) 在 1,6-二烯/乙醚混合物 (1, 6-二烯 = 庚-1,6-二烯、二烯丙基醚、dvds (1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷)) 得到分离的均质双核 Pd0 和 Pt0 化合物 Pd2(C7H12)3 ( 1)、Pd2(C6H10O)3·C6H10O(2'；2：Pd2(C6H10O)3)、Pd2(dvds)3(3)和Pt2(C7H12)3(4)。当 1-4 用额外的 1,6-二烯处理时，M(1,6-二烯)2 (5-8) 型的同样均质但单核的衍生物和乙烯混合烯烃配合物 (C2H4)M(1,6 -二烯) (9-12) 在溶液中获得。配合物 1-12 与供体配体如膦、亚磷酸盐或 tBuNC
• Suzuki-Miyaura Cross-Coupling Reactions of Highly Fluorinated Arylboronic Esters: Catalytic Studies and Stoichiometric Model Reactions on the Transmetallation Step
  作者：Johannes Kohlmann、Thomas Braun、Reik Laubenstein、Roy Herrmann

  DOI：10.1002/chem.201700549

  日期：2017.9.7

  Deserves a metal: The Suzuki–Miyaura cross-coupling reaction of highly fluorinated boronic esters, such as 2-Bpin-C5NF4, was investigated by using [Pd(Me)2(tmeda)] or trans-[PdBr4-C6H4CH2CHNHC(O)CH3}CO2Et}(PiPr3)2] as precatalysts. Stoichiometric studies on the transmetallation step revealed the high reactivity of a Pd fluorido derivative towards 2-BpinC5NF4, which leads to the formation of an ionic

  值得一金属：高度氟化的硼酸酯的Suzuki-Miyaura交叉偶联反应，例如2- BPIN-C 5 NF 4，通过使用研究[钯（ME）2（TMEDA）]或反式- [PDBR 4 -C 6 H 4 CH 2 CH NHC（O）CH 3 } CO 2 Et}（P i Pr 3）2 ]作为预催化剂。关于金属转移步骤的化学计量研究表明，Pd氟代衍生物对2-BpinC 5 NF 4具有高反应活性，这导致离子中间体的形成并最终产生交叉偶联产物。
• The Impact of Palladium(II) Reduction Pathways on the Structure and Activity of Palladium(0) Catalysts
  作者：Carolyn S. Wei、Geraint H. M. Davies、Omid Soltani、Jacob Albrecht、Qi Gao、Charles Pathirana、Yi Hsiao、Srinivas Tummala、Martin D. Eastgate

  DOI：10.1002/anie.201210252

  日期：2013.5.27

  Two roads diverged: The mechanism of in situ PdII catalyst activation to generate an active LnPd0} catalyst from an air‐stable PdII precursor was examined using the standard conditions of a Miyaura borylation reaction. Two pathways for catalyst activation exist under these conditions, producing two structurally and chemically distinct LnPd0} complexes (see scheme).

  两条道路分歧：使用Miyaura硼化反应的标准条件，研究了原位Pd II催化剂活化从空气稳定的Pd II前体生成活性L n Pd 0 }催化剂的机理。在这些条件下存在两种催化剂活化途径，产生两种结构和化学上不同的L n Pd 0 }配合物（参见方案）。
• Synthesis and reactivity of a cationic palladium complex as possible intermediate in a Suzuki-Miyaura cross-coupling reaction
  作者：Johannes Kohlmann、Thomas Braun

  DOI：10.1016/j.jfluchem.2017.08.003

  日期：2017.11

  A stoichiometric reaction of a palladium fluorido complex with an aromatic boronic ester yielded a fluorinated 4-aryl phenylalanine derivative (aryl = 4-C6H4SF5) as Suzuki-Miyaura cross-coupling product. Due to the high reactivity of the metal complex, the reaction proceeded smoothly at ambient temperature. Low-temperature NMR investigations revealed a possible role of trans‐[PdBF(4-C6H4SF5)(pin)}(PheEt)(PiPr3)2]

  钯氟化物络合物与芳族硼酸酯的化学计量反应产生了作为铃木-宫浦交叉偶联产物的氟化4-芳基苯丙氨酸衍生物（芳基= 4-C 6 H 4 SF 5）。由于金属络合物的高反应性，该反应在环境温度下顺利进行。低温NMR研究揭示了反式[Pd BF（4-C 6 H 4 SF 5）（pin）}（Phe Et）（P i Pr 3）2 ]的可能作用（5，Phe Et  =结合的苯丙氨酸导数= 4-C 6 H 4作为过渡金属化步骤的潜在中间产物，CH 2 C NHC（O）CH 3 }（CO 2 Et）2，pin = pinacolato = O 2 C 2 Me 4）。化合物5是由氟化物从钯到硼的转移而产生的。在用NaBF 4处理氟代络合物时，生成了类似的络合物反式[[Pd（BF 4）（Phe Et）（P i Pr 3）2 ]（7）。配合物7在室温下不稳定。降解得到the盐[P iPr 3 Phe Et ] [BF
• Isolation and reactivity of palladium hydrido complexes: intermediates in the hydrodefluorination of pentafluoropyridine
  作者：David Breyer、Thomas Braun、Anna Penner

  DOI：10.1039/c0dt00086h

  日期：——

  The hydrido complexes trans-[Pd(H)(4-C5NF4)(PiPr3)2] (3) and trans-[Pd(H)(4-C5NF4)(PCy3)2] (5) can be prepared by reaction of trans-[Pd(F)(4-C5NF4)(PiPr3)2] (2) or trans-[Pd(F)(4-C5NF4)(PCy3)2] (4) with HBpin (HBpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, pinacolborane). The iodo and triflato complexes trans-[Pd(I)(4-C5NF4)(PiPr3)2] (7) and trans-[Pd(OTf)(4-C5NF4)(PiPr3)2] (9) are generated on treatment

  氢化物反式-[Pd（H）（4-C 5 NF 4）（P i Pr 3）2 ]（3）和反式-[Pd（H）（4-C 5 NF 4）（PCy 3）2 ]（5）可通过反式-[Pd（F）（4-C 5 NF 4）（P i Pr 3）2 ]（2）或反式-[Pd（F）（4-C 5 NF ）反应制备4）（PCy 3）2 ]（4）与HBpin（HBpin =4,4,5,5-四甲基-1,3,2-二氧杂硼烷，频哪醇硼烷）。碘酒和Triflato配合物的反式- [钯（I）（4-C 5 NF 4）（P我镨3）2 ]（7）和反式- [钯（OTF）（4-C 5 NF 4）（P我镨3）2 ]（9）是在治疗的复杂产生3与I 或者 三氟甲磺酸乙酯 （OT）， 分别。治疗3的Ph 3 CPF 6中机械化结果形成反式-[Pd（4-C 5 NF 4）（NCMe）（P i Pr 3）2 ] PF 6（6a）。加热3至60°C可消除还原产物2