Table 1. Reaction Optimization.
no.a | solvent | 4a:5a ratio | other | yield (%) |
---|---|---|---|---|
1 | toluene | 1:2 | 50 | |
2 | n-hexane | 1:2 | 24 | |
3 | CHCl3 | 1:2 | 68 | |
4 | DCM | 1:2 | 80 | |
5 | 1,2-DCE | 1:2 | 73 | |
6 | EtOAc | 1:2 | 67 | |
7 | CH3CN | 1:2 | 69 | |
8 | THF | 1:2 | 67 | |
9 | DCM | 1:4 | 60 | |
10 | DCM | 1:1 | 76 | |
11 | DCM | 2:1 | 55 | |
12b | DCM | 1:2 | slow add. | 83 |
13 | DCM | 1:2 | 0.5 mL | 76 |
14 | DCM | 1:2 | 2 mL | 71 |
15c | DCM | 1:2 | dark | no reaction |
Reaction conditions: 4a (0.4 mmol) and 5a (0.8 mmol) were dissolved in 1 mL of solvent and were irradiated at room temperature with blue LEDs (1 W, 470 nm) overnight (16 h).
4a and 5a were each dissolved in 0.5 mL of DCM, 5a being slowly added over the course of 6 h by a syringe pump, under otherwise identical conditions.
The reaction mixture was stirred in the dark.