ABSTRACT
New acylhydrazone-based palladacycles are prepared and evaluated as pre-catalysts in Mirozoki-Heck and oxyarylation reactions.
Key words:
acylhydrazone; palladacycle; Mirozoki-Heck reaction; oxyarylation
New acylhydrazone-based palladacycles are prepared and evaluated as pre-catalysts in Mirozoki-Heck and oxyarylation reactions.
Key words:
acylhydrazone; palladacycle; Mirozoki-Heck reaction; oxyarylation
entry | Solvent | Base | Pd(mol%) | T( o C) | Time (h) | Yield (%) |
1 | DMF | TEA | 0.1(2a) | 110 | 10 | 96 |
2 | DMF | TEA | 0.1(2b) | 110 | 10 | 98 |
3 | DMF | TEA | 0.1(2c) | 110 | 10 | 98 |
4 | DMF | TEA | 0.001(2a) | 110 | 24 | 80 |
5 | DMF | TEA | 0.001(2b) | 110 | 24 | 95 |
6 | DMF | TEA | 0.001(1c) | 110 | 24 | 95 |
7 | DMF | DIPEA | 0.001(2a) | 110 | 24 | 85 |
8 | DMF | DIPEA | 0.001(2b) | 110 | 24 | 80 |
9 | DMF | Na2CO3 | 0.001(2a) | 110 | 24 | 65 |
10 | DMF | Na2CO3 | 0.001(2b) | 110 | 24 | 72 |
11 | DMF | Na2CO3 | 0.001(2c) | 110 | 24 | 70 |
12 | MeCN | TEA | 0.001(2a) | 80 | 24 | 90 |
13 | MeCN | TEA | 0.001(2b) | 80 | 24 | 92 |
14 | MeCN | TEA | 0.001(2c) | 80 | 24 | 92 |
15 | NMP | TEA | 0.001(2b) | 110 | 24 | 80 |
16 | NMP | TEA | 0.001(1c) | 110 | 24 | 75 |
entry | Solvent | Base | Pd (mol%) | T ( o C) | Time (h) | Yield (%) |
1 | DMF | TEA | 0.1(2b) | 110 | 24 | 67 |
2 | DMF | TEA | 0.1(2c) | 110 | 24 | 60 |
3 | DMF | TEA | 0.001(2b) | 110 | 24 | 50 |
4 | DMF | TEA | 0.001(2c) | 110 | 24 | 45 |
entry | ArI | Pd (1mol%) | Product | T (o C) | Time (h) | Yield (%) |
---|---|---|---|---|---|---|
1 | 9a | 2a | 11a | 120 | 12 | 50 |
2 | 9a | 2b | 11a | 120 | 12 | 55 |
3 | 9a | 2c | 11a | 120 | 12 | 56 |
4 | 9b | 2c | 10b | 120 | 12 | 52 |
5 | 9c | 2c | 10c | 120 | 12 | 53 |