Optimization of the catalytic oxidation of benzyl alcohol and reduction of nitrobenzene using 10 and 11, respectively.
| Entry | Solvent | C–C Suzuki couplinga | C–N couplingb | |||||
|---|---|---|---|---|---|---|---|---|
| T (°C) | Cat. 11 (mg) | Yield (%) | T (°C) | NaBH4 (mmol) | Cat. 11 (mg) | Yield (%) | ||
| 1 | EtOH | Ref. | 1.0 | 55 | Ref. | 2.0 | 2.0 | 50 |
| 2 | MeOH | Ref. | 1.0 | 60 | Ref. | 2.0 | 2.0 | 50 |
| 3 | THF | Ref. | 1.0 | N.R. | Ref. | 2.0 | 2.0 | N.R. |
| 4 | CH3CN | Ref. | 1.0 | 55 | Ref. | 2.0 | 2.0 | 40 |
| 5 | DMF | Ref. | 1.0 | 80 | Ref. | 2.0 | 2.0 | 88 |
| 6 | Glycerol | 120 | 1.0 | 84 | 160 | 2.0 | 2.0 | 85 |
| 7 | Dioxane | Ref. | 1.0 | 30 | Ref. | 2.0 | 2.0 | 45 |
| 8 | Toluene | Ref. | 1.0 | 55 | Ref. | 2.0 | 2.0 | 60 |
| 9 | H2O | Ref. | 1.0 | 45 | Ref. | 2.0 | 2.0 | 30 |
| 10 | DMSO | Ref. | 1.0 | 80 | Ref. | 2.0 | 2.0 | 90 |
| 11 | DMSO 2 | 120 | 1.0 | 84 | 120 c | 2.0 | 2.0 | 90 d |
| 12 | DMSO2 | 80 | 1.0 | 44 | 80 | 2.0 | 2.0 | 60 |
| 13 | DMSO2 | 160 | 1.0 | 85 | 160 | 2.0 | 2.0 | 90 |
| 14 | DMSO2 | R.T. | 1.0 | N.R. | Ref. | 1.0 | 2.0 | 33 |
| 15 | DMSO2 | Ref. | 0.001 | 50 | Ref. | 1.5 | 2.0 | 55 |
| 16 | DMSO2 | Ref. | 0.05 | 68 | Ref. | 2.0 | 0.5 | 65 |
| 17 | DMSO2 | Ref. | 1.5 | 80 | Ref. | 2.0 | 1.0 | 80 |
| 18 | DMSO2 | Ref. | 2.0 | 84 | Ref. | 2.0 | 2.5 | 90 |
| 19e | DMSO2 | 120 | 1.0 | 30 | 120 | 0 | 2.0 | N.R. |
Reaction conditions: benzyl alcohol (1.0 mmol), catalyst 11, temperature, solvent (2.0 mL, DMSO2: 3.36 g), O2 balloon (∼1.0 atm). For a better comparison, a constant time of 33 h was reported for all entries.
Reaction conditions: nitrobenzene (1.0 mmol), NaBH4 (2.0 mmol), catalyst 11, solvent (2.0 mL, DMSO2: 3.36 g). For the better comparison, a constant time of 4.2 h was reported for all entries.
No improvement was observed until 40 h.
No improvement was observed until 8 h.
The reaction was performed under air conditions.