Table 4. Optimization of reaction conditions for aerobic dehydrogenation of 1,4-dihydropyridines with CuMnFe-LDHzymea.
| |||||
|---|---|---|---|---|---|
| Entry | Mediator (mol%) | Amount of CuMnFe-LDHzyme | Temperature (°C) | Solvent | Yield (%) |
| 1 | — | 130 | 50 | CH3CN | 55 |
| 2 | DDQ (5) | 130 | 50 | CH3CN | 55 |
| 3 | 4-Phenyl urazole (5) | 110 | 50 | CH3CN | 58 |
| 4 | DDQ (10) | 130 | 50 | CH 3 CN | 95 |
| 5 | 4-Phenyl urazole (10) | 110 | 50 | CH 3 CN | 95 |
| 6 | DDQ (10) | — | 50 | CH3CN | 45 |
| 7 | 4-Phenyl urazole (10) | — | 50 | CH3CN | Trace |
| 8 | DDQ (10) | 100 | 50 | CH3CN | 70 |
| 9 | DDQ (10) | 120 | 50 | CH3CN | 83 |
| 10 | 4-Phenyl urazole (10) | 100 | 50 | CH3CN | 85 |
| 11 | DDQ (10) | 130 | 50 | H2O | 35 |
| 12 | DDQ (10) | 130 | 50 | DMSO | 45 |
| 13 | 4-Phenyl urazole (10) | 110 | 50 | H2O | 37 |
| 14 | 4-Phenyl urazole (10) | 110 | 50 | DMSO | 60 |
| 15 | DDQ (10) | 130 | 40 | CH3CN | 70 |
| 16 | 4-Phenyl urazole (10) | 110 | 40 | CH3CN | 60 |
Reaction conditions: CuMnFe-LDHzyme (130 mg), substrate (1 mmol), mediator (10 mol%), solvent (3 mL), molecular oxygen (balloon) 20 h; the bold represented the most effective reaction conditions.