Table 3.
Optimization of conditions for arylative cyclization of 1a.
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# | [Pd] source | Ligand | Base | Temperature | 12a:13a Ratioa | Yield of 12a, %b |
1 | Pd(OAc)2 | dppp | KOAc | 120 | - | 0 |
2 | Pd(OAc)2 | dppe | KOAc | 120 | - | 0 |
3 | Pd(OAc)2 | Ph2P(CH2)5PPh2 | KOAc | 120 | - | 0 |
4 | Pd(OAc)2 | dppf | KOAc | 100 | 90:10 | 10 |
5 | Pd(OAc)2 | d-t-Bupf | KOAc | 100 | 90:10 | 12 |
6 | Pd(OAc)2 | d-i-Prpf | KOAc | 120 | 95:5 | 12 |
7 | Pd(OAc)2 | d-i-Prpf | Cs2CO3 | 120 | - | 0 |
8 | Pd(OAc)2 | d-i-Prpf | Et3N | 120 | 99:1 | 45 |
9 | Pd(OAc)2 | d-i-Prpf | EtN(i-Pr)2 | 120 | 100:0 | 60 |
10 | PdCl2 | d-i-Prpf | EtN(i-Pr)2 | 120 | 100:0 | 31 |
11 | Pd(dba)2 | d-i-Prpf | EtN(i-Pr)2 | 120 | 100:0 | 20 |
12 | PdCl2(CH3CN)2 | d-i-Prpf | EtN(i-Pr)2 | 120 | 100:0 | 30 |
13 | Pd(OAc)2 | d-i-Prpf | Bu4NBr | 120 | 100:0 | 20 |
14 | Pd(OAc)2 | d-i-Prpf | DABCO | 100 | 100:0 | 70c |
15 | Pd(OAc)2 | dppf | DABCO | 110 | 100:0 | 81 |
16 | Pd(OAc)2 | d-t-Bupf | DABCO | 110 | 100:0 | 80 |
17 | Pd(OAc)2 | d-i-Prpf | DABCO | 110 | 100:0 | 95 |
18 | Pd(OAc)2 | d-i-Prpf | DABCO | 120 | 100:0 | 89d |
Product ratios determined by GC/MS analysis.
Yield determined by GC/MS analysis.
Yield after 24 hrs.
Isolated yield after 6 hrs.