Table 1. Optimization of the Reaction Conditionsa.
entry | catalyst (mol %) | base (3 equiv) | solvent | temp (°C) | oxidant | yield (%) 3a |
---|---|---|---|---|---|---|
1 | I2 (20) | H2O | rt | air | 32 | |
2 | I2 (30) | H2O | rt | air | 38 | |
3 | I2 (40) | H2O | rt | air | 39 | |
4 | I2 (30) | H2O | 50 | air | 62 | |
5 | I2 (30) | H2O | 60 | air | 65 | |
6 | I2 (30) | H2O | 70 | air | 71 | |
7 | I2 (30) | H2O | 80 | air | 71 | |
8 | I2 (30) | K2CO3 | H2O | 70 | air | 94 |
9 | I2 (30) | NaHCO3 | H2O | 70 | air | 69 |
10 | I2 (30) | Na2CO3 | H2O | 70 | air | 74 |
11 | I2 (30) | Cs2CO3 | H2O | 70 | air | trace |
12 | I2 (30) | TEA | H2O | 70 | air | trace |
13 | I2 (30) | DBU | H2O | 70 | air | trace |
14 | I2 (30) | pyridine | H2O | 70 | air | trace |
15 | I2 (30) | K2CO3 | H2O | 70 | N2-atm | 0 |
16 | K2CO3 | H2O | 70 | air | 0 | |
17 | TBAI | K2CO3 | H2O | 70 | air | trace |
18 | KI | K2CO3 | H2O | 70 | air | trace |
Reaction conditions: 1a (0.5 mmol, 1 equiv), 2a (1.0 mmol, 2 equiv), catalyst (0.15 mmol, 0.3 equiv) in solvent (2.0 mL) for 6 h; H2O = water, rt = room temperature.