A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterization
2.2. Investigation on the Catalytic Activity of Complex 1 in the Allylic Oxidation of Alkenes
2.3. X-ray Crystallography
3. Experimental Section
3.1. Materials and Instruments
3.2. Synthesis
3.2.1. Synthesis of HC(COOHex)(pz)2 (LOHex)
3.2.2. Synthesis of [Cu(LOHex)Br(μ-Br)]2 (1)
3.2.3. General Procedure for the Synthesis of Compounds 4–6
Synthesis of 4
Synthesis of 5
Synthesis of 6
3.3. Crystallographic Data Collection and Refinement
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Entry | 1 mol% | 2:3 Ratio | Reaction Time (h) | Yield (%) a 4 |
---|---|---|---|---|
1a | 5 | 5:1 | 6 | 73 |
1b | 5 | 5:1 | 24 | 95 |
1c | 5 | 3:1 | 24 | 79 |
1d | 1 | 5:1 | 24 | 77 |
1e | 1 | 3:1 | 24 | 74 |
1f | 0.5 | 10:1 | 24 | 95 |
1g | 0.5 | 5:1 | 24 | 90 |
1h | 0.5 | 3:1 | 24 | 90 |
1i | 0.5 | 1:1 | 48 | 33 |
Catalyst Type | Reaction Conditions | Yield (%) | Ref. | |
---|---|---|---|---|
Cu(I) and Cu(II) salts | 5 mol% cat., 32–48 h, PhNHNH2 (6 μL), CH3CN (3 mL), reflux | 85 (n = 1) 92 (n = 2) 76 (n = 4) | [76] | |
Cu(CH3CN)4PF6 immobilized on halloysite | 20 mg cat., 7–45 h, CH3CN (3 mL), r.t. | 67 (n = 1) 90 (n = 2) 80 (n = 4) | [77] | |
Cu(I) and Cu(II) complexes | 2.5 mol% Cu salt, 5 mol% chiral ligand, 50–81 h, PhNHNH2 (2 μL), HZSM-5 (5 mg), acetone, 0 °C | 75 (n = 1) 85 (n = 3) 75 (n = 4) | [78] | |
Cu(II) complexes | 1 mol% Cu(OTf)2, 1.1 mol% chiral ligand, 0.5–168 h, 1.1 mol% PhNHNH2, acetone, r.t. | 78 (n = 1) 82 (n = 2) 81 (n = 3) 0 (n = 4) | [79] | |
CuBr | 10 mol% CuBr, 18 h, dichlorobenzene, 70 °C, inert atm. | 70 (n = 2) | [9] |
Bond | Bond Length (Å) | Bond | Bond Length (Å) |
Br(1)−Cu(1) | 2.4302 (4) | Br(2)−Cu(1) | 2.3687 (6) |
Br(1)−Cu(1) I | 2.7600 (5) | Cu(1)−N(1) | 2.017 (2) |
Cu(1)−N(3) | 2.042 (3) | N(1)−N(2) | 1.357 (3) |
N(3)−N(4) | 1.369 (3) | N(1)−C(3) | 1.330 (4) |
N(2)−C(1) | 1.342 (4) | N(3)−C(6) | 1.305 (4) |
N(4)−C(4) | 1.338 (4) | N(2)−C(7) | 1.445 (3) |
N(4)−C(7) | 1.434 (4) | C(1)−C(2) | 1.344 (5) |
C(2)−C(3) | 1.384 (5) | C(4)−C(5) | 1.355 (5) |
C(5)−C(6) | 1.399 (5) | C(7)−C(8) | 1.533 (4) |
O(1)−C(8) | 1.198 (3) | O(2)−C(8) | 1.310 (4) |
Bond | Bond Angle (°) | Bond | Bond Angle (°) |
Cu(1)−Br(1)−Cu(1) I | 93.544 (13) | Br(1)−Cu(1)−Br(1) I | 86.456 (13) |
N(1)−Cu(1)−Br(1) I | 93.87 (7) | N(3)−Cu(1)−Br(1) I | 97.29 (7) |
Br(2)−Cu(1)−Br(1) | 93.260 (18) | N(1)−Cu(1)−Br(1) | 176.35 (7) |
N(3)−Cu(1)−Br(2) | 157.34 (7) | N(1)−Cu(1)−N(3) | 85.69 (10) |
N(1)−Cu(1)−Br(2) | 90.16 (8) | N(3)−Cu(1)−Br(1) | 90.67 (7) |
N(2)−N(1)−Cu(1) | 122.68 (17) | N(4)−N(3)−Cu(1) | 121.3 (2) |
N(1)−N(2)−C(7) | 118.8 (2) | N(3)−N(4)−C(7) | 119.4 (2) |
N(1)−C(3)−C(2) | 110.6 (3) | N(3)−C(6)−C(5) | 111.5 (3) |
C(1)−N(2)−N(1) | 111.2 (2) | C(4)−N(4)−N(3) | 110.6 (3) |
N(2)−C(1)−C(2) | 107.3 (3) | N(4)−C(4)−C(5) | 107.9 (3) |
N(4)−C(7)−N(2) | 110.1 (2) | C(1)−C(2)−C(3) | 106.2 (3) |
C(4)−C(5)−C(6) | 104.8 (4) | O(2)−C(8)−C(7) | 108.8 (2) |
O(1)−C(8)−C(7) | 124.6 (3) | O(1)−C(8)−O(2) | 126.6 (3) |
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Bagnarelli, L.; Dolmella, A.; Santini, C.; Vallesi, R.; Giacomantonio, R.; Gabrielli, S.; Pellei, M. A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations. Molecules 2021, 26, 6271. https://doi.org/10.3390/molecules26206271
Bagnarelli L, Dolmella A, Santini C, Vallesi R, Giacomantonio R, Gabrielli S, Pellei M. A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations. Molecules. 2021; 26(20):6271. https://doi.org/10.3390/molecules26206271
Chicago/Turabian StyleBagnarelli, Luca, Alessandro Dolmella, Carlo Santini, Riccardo Vallesi, Roberto Giacomantonio, Serena Gabrielli, and Maura Pellei. 2021. "A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations" Molecules 26, no. 20: 6271. https://doi.org/10.3390/molecules26206271