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Table 1 Pd-catalyzed borylation of 4-chloroanisole (1a) under various conditions

From: Palladium-catalyzed borylation of aryl (pseudo)halides and its applications in biaryl synthesis

Entry Catalyst Solvent Base Temp. (°C) Time (h) Yielda (%)
1 Pd(PPh3) 4 b DMSO KOAc 80 8 Tracec
2 Pd(PPh3)4/PCy 3 b Dioxane KOAc 80 8 72c
3 PdCl2(PPh3) 2 b DMF K3PO4 80 8 12c
4 PdCl2(dppf)b DMF K3PO4 80 8 Tracec
5 PdCl2(dppf)b DMSO KOAc 80 8 Tracec
6 Pd2dba3/PCy 3 b Dioxane KOAc 110 8 67c
7 Pd2dba3/XPhosb Dioxane KOAc 110 8 81c
8 Pd2dba3/SPhosb Dioxane KOAc 110 8 48c
9 Pd(OAc)2/PCy 3 b Dioxane KOAc 110 2 69c
10 Pd(OAc)2/XPhosb Dioxane KOAc 110 2 76c
11 Pd(OAc)2/SPhos Dioxane KOAc RT 48 42
12 9a THF KOAc RT 2 Traced
13 9a EtOH KOAc RT 2 13d
14 9b THF KOAc RT 2 23d
15 9b EtOH KOAc RT 2 66d
16 10a THF KOAc RT 2 21d
17 10a EtOH KOAc RT 2 12d
18 10b THF KOAc RT 2 93d
19 10b EtOH KOAc RT 2 35
20 10b THF K3PO4 RT 1 87e, 98f
  1. Reaction conditions: 4-chloroanisole (1a; 1.0 mmol), B2pin2 (3.0 mmol), base (3.0 mmol), catalyst (2.0 mol%), ligand (4.0 mol%), solvent (2 mL)
  2. aIsolated yield
  3. bNo reaction occurred at room temperature
  4. cSealed tube
  5. dB2pin2 (3.0 mmol), precatalyst (2.0 mol%)
  6. eB2pin2 (3.0 mmol), precatalyst (2.0 mol%), K3PO4 (2.0 mmol)
  7. fB2pin2 (1.2 mmol), precatalyst (1.0 mol%)