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Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions

A technology of heterocyclic carbene and reaction, applied in the field of manufacturing these complexes, can solve the problems of laborious synthesis, difficulty, high cost, etc., and achieve the effect of low catalyst concentration

Inactive Publication Date: 2008-05-21
PROMERUS LLC
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These issues include (i) relatively difficult or laborious synthesis, (ii) expensive catalyst precursors and / or ligand sets, (iii) oxygen and water sensitivity of ligands or metal catalysts, (iv) difficulty in optimizing activity, Because of the completely different precatalyst structures and uncommon and non-modular ligands, and (v) the catalysts used to activate aryl chlorides need to be used in relatively high concentrations

Method used

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  • Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions
  • Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions
  • Nucleophilic heterocyclic carbene derivatives of pd(acac)2 for cross-coupling reactions

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0160] Example 1 Synthesis of (IPr)Pd(acac) 2 (Pd complex 1)

[0161] In the glove box, to a Schlenk flask equipped with a magnetic bar was added free carbene IPr (855 mg, 2.2 mmol), Pd(acac) 2 (609mg, 2mmol) and anhydrous toluene (30mL), sealed with a rubber cap. The mixture was stirred at room temperature for 2 hours. The solvent was evaporated in vacuo and THF (25 mL) was added. The solution was filtered and the solid was washed with THF (2 x 5 mL). The solvent was evaporated in vacuo; the complex was then triturated with cold pentane (25 mL), and the solution was filtered. Recrystallization from a chloroform / pentane mixture (25 / 75) gave 1.28 g (93%) of the title compound. 1 H-NMR (400MHz, C 6 D. 6 ): δ7.28-7.24(m, 2H), 7.18(d, J=8.0Hz, 4H), 6.47(s, 2H), 5.90(s, 1H), 4.78(s, 1H), 2.88(q, J=6.8 Hz, 4H), 2.63(d, J=0.8Hz, 3H), 2.01(d, J=0.8Hz, 3H), 1.63(s, 3H), 1.35(d, J=6.8, 12H), 1.31 (s, 3H), 0.97 (d, J=6.8, 12H). 13 C-NMR (100MHz, C 6 D. 6 ): 207.5, 192.9, 188....

Embodiment 2

[0162] Example 2 One-pot synthesis of (IPr)Pd(acac)Cl (Pd complex 2)

[0163] In the glove box, add free carbene IPr (2.73 g, 7 mmol), Pd(acac) to a Schlenk flask equipped with a magnetic bar 2 (1.53g, 5mmol) and dry dioxane (50mL), sealed with a rubber cap. The mixture was stirred at room temperature for 2 hours. Then, 1.25 mL of HCl in 4M dioxane was injected into the solution, and the mixture was stirred at room temperature for another 2 hours. The solvent was then evaporated in vacuo and diethyl ether was added until no more solid dissolved (20 mL). The solution was filtered and the solid was washed with ether (2 x 10 mL). The solvent was evaporated in vacuo and the resulting powder was kept under vacuum overnight to yield 2.85 g (90%) of the title product. 1 H-NMR (400MHz, CDCl 3 ): δ7.51(t, J=7.6Hz, 2H), 7.35(d, J=8Hz, 4H), 7.12(s, 2H), 5.12(s, 1H), 2.95(q, J=6.4Hz, 4H), 1.84(s, 3H), 1.82(s, 3H), 1.34(d, J=6.4Hz, 12H), 1.10(d, J=6.4Hz, 12H). 13 C-NMR (100MHz, CDCl...

Embodiment 3

[0164] Example 3 One-pot synthesis of (IPr)Pd(acac)Cl (Pd complex 2)

[0165] In the glove box, add imidazolium salt IPr HCl (2.96 g, 7 mmol), Pd(acac) to a Schlenk flask equipped with a magnetic bar 2 (1.53g, 5mmol) and anhydrous dioxane (100mL). The flask was taken out from the glove box, placed in an oil bath at 100°C, and stirred with a magnetic stirrer for 6 hours. The solution then appeared clear with no solids remaining. The solvent was evaporated in vacuo and diethyl ether was added until no more solids dissolved. The solution was filtered and the solid was washed with ether (2 x 10 mL). The solvent was evaporated in vacuo to afford 2.99 g (95%) of the title compound as a yellow powder.

[0166] 1 H NMR (δ, 400MHz, CDCl 3 ): 7.51(t, J=7.8Hz, 2H), 7.35(d, J=7.8Hz, 4H), 7.12(s, 2H), 5.12(s, 1H), 2.95(q, J=6.4Hz, 4H ), 1.84 (s, 3H), 1.82 (s, 3H), 1.34 (d, J=6.4Hz, 12H), 1.10 (d, J=6.4Hz, 12H).

[0167] 13 C NMR (δ, 100MHz, CDCl 3 ): 187.1, 184.1, 156.4, 147.0, 1...

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Abstract

Embodiments in accordance with the present invention provide for a palladium complex characterized by the general Formula (I): where A is a bidentate monoanionic ligand, NHC is a nucleophilic heterocyclic carbene, and Z is an anionic ligand. Such palladium complexes are useful in initiating cross-coupling reactions.

Description

[0001] Cross References to Related Applications [0002] This application claims the benefit of U.S. Provisional Application No. 60 / 788,989, filed April 4, 2006, and U.S. Provisional Application No. 60 / 685,620, filed May 27, 2005, both of which are incorporated herein in their entirety Reference. technical field [0003] The present invention relates generally to palladium complexes with bidentate monoanionic ligands, nucleophilic heterocyclic carbene (NHC), and anionic ligands for use in carbon-carbon and carbon-heteroatom bond forming reactions, and the manufacture of these complex method. Background technique [0004] Palladium-catalyzed carbon-carbon and carbon-heteroatom bond formation reactions, hereinafter also referred to as cross-coupling reactions, such as but not limited to conventional reactions such as Suzuki-Miyaura, Stille, Heck, Sonagashira, Negishi, Kumada cross-coupling, Buchwald- Hartwig aminations, catalyzed ether formation, catalyzed α-arylation of ket...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C5/00C07C5/02C07C43/15C07C209/08C07C209/22
Inventor 迪诺·阿莫罗索安德鲁·贝尔奥斯卡·纳瓦洛·费尔南德斯尼古拉斯·马里恩史蒂文·P·诺兰
Owner PROMERUS LLC
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