Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Materials
3.2. Synthesis of Pyrazolyl Analogues of DPEphos and tBu-Xantphos
3.2.1. Dibromination of p-Tolyl Ether (Preparation of 1)
3.2.2. Preparation of 3-Mesityl-1H-pyrazole
3.2.3. Synthesis of Ligands 1a and 1a`
3.2.4. Synthesis of Ligands 2a and 2a`
3.2.5. Synthesis of Ligands 2b and 2b`
3.2.6. Synthesis of hybrid Ligand 2b`c
3.2.7. Synthesis of Hybrid Ligand 2a`d
3.3. X-ray Crystallography of 1, 1a, 2a, 2b and 2b`
3.4. General Procedure for SM Cross-Coupling Reaction
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Entry | [Pd] (1 mol%) | Base | Solvent | Conversion (%) b | CC Yield (%) b | HC Yield (%) c |
---|---|---|---|---|---|---|
1 | Pd(OAc)2 | KOH | MeOH | 74 | 66 | 1 |
2 | Pd(OAc)2 | K3PO4 | Dioxane | 48 | 7 | 1 |
3 | Pd(OAc)2 | Cs2CO3 | DMF | 87 | 61 | 1 |
4 | Pd(OAc)2 | K2CO3 | DMF | 99 | 98 | 1 |
5 | Pd(OAc)2 | K2CO3 | MeOH | 75 | 44 | 1 |
6 | Pd(OAc)2 | K2CO3 | THF:MeOH d | 65 | 4 | 2 |
7 | Pd(OAc)2 | K2CO3 | THF d | 49 | 1 | 2 |
8 | Pd(OAc)2 | K2CO3 | Dioxane | 48 | 2 | 1 |
9 | PdCl2 | K2CO3 | DMF | 97 | 88 | 4 |
10 | PdCl2(COD) e | K2CO3 | DMF | 72 | 55 | 3 |
11 | PdCl2(PhCN)2 | K2CO3 | DMF | 93 | 92 | 2 |
Entry | Temp. (°C) | Time (h) | Conversion (%) b | CC Yield (%) b | HC Yield (%) c |
---|---|---|---|---|---|
1 | 25 | 24 | 73 | 59 | 1 |
2 | 50 | 12 | 92 | 70 | 1 |
3 | 80 | 6 | 99 | 98 | 1 |
4 | 110 | 3 | 90 | 75 | 1 |
5 | 80 | 12 | 87 | 82 d | 1 |
Entry | Ligand | Conversion (%) b | CC Yield (%) b | HC Yield (%) c |
---|---|---|---|---|
1 | 2a | 99 | 98 | 1 |
2 | 2b | >99 | 98 | 1 |
3 | 2b`c | 99 | 98 | 1 |
4 | 2a` | 87 | 86 | 1 |
5 | 2a`d | 46 | 5 | 1 |
6 | 1a | 83 | 47 | 1 |
7 | 1a` | 62 | 29 | 1 |
8 | - | 68 | 44 | 2 |
9 | Xantphos | 84 | 77 | 6 |
Entry | R1 | X | R2 | Yield (%) b |
---|---|---|---|---|
1 | 4-Me | Br | H | 94 |
2 | 4-CF3 | Br | H | 82 |
3 | 4-Ac | Br | H | 92 |
4 | 4-Ome | Br | H | 91 |
5 | 2-bromonaphthalene | H | 91 | |
6 | 4-Me | Br | 4-OMe | 82 |
7 | 4-Me | Br | 4-Ac | 78 |
8 | 4-OMe | Br | 4-Ac | 73 |
9 | 4-Ac | Br | 4-Me | 81 |
10 | 2-Me | Br | H | 58 |
11 | 4-Me | Br | 2-Me | 54 |
12 | 4-Me | Br | 2,6-diMe | 46 |
13 | 4-CF3 | I | H | 78 |
14 | 4-OMe | I | H | 80 |
15 | 4-Ac | Cl | H | 75 |
16 | 4-Ac | Cl | H | 3 c |
17 | 4-Me | Cl | H | 25 |
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Hussain, Z.; Schwalm, C.; Rambo, R.; Dias, R.; Stieler, R.; Monteiro, A. Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction. Catalysts 2019, 9, 718. https://doi.org/10.3390/catal9090718
Hussain Z, Schwalm C, Rambo R, Dias R, Stieler R, Monteiro A. Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction. Catalysts. 2019; 9(9):718. https://doi.org/10.3390/catal9090718
Chicago/Turabian StyleHussain, Zahid, Cristiane Schwalm, Raoní Rambo, Renieidy Dias, Rafael Stieler, and Adriano Monteiro. 2019. "Synthesis of Mono- and Bis-Pyrazoles Bearing Flexible p-Tolyl Ether and Rigid Xanthene Backbones, and Their Potential as Ligands in the Pd-Catalysed Suzuki–Miyaura Cross-Coupling Reaction" Catalysts 9, no. 9: 718. https://doi.org/10.3390/catal9090718