Table 1. Optimization of Pd-Catalyzed Decarbonylative Borylation of Amides^a.

entry	catalyst	ligand	base	yieldb (%)
1	Pd(OAc)2	PPh3	Na2CO3	15
2	Pd(OAc)2	P(4-MeO-C6H4)3	Na2CO3	27
3	Pd(OAc)2	P(4-CF3-C6H4)3	Na2CO3	12
4	Pd(OAc)2	PCyPh2	Na2CO3	24
5	Pd(OAc)2	PCy2Ph	Na2CO3	28
6	Pd(OAc)2	PCy3HBF4	Na2CO3	49
7	Pd(OAc)2	Dppb	Na2CO3	5
8	Pd(OAc)2	Dppp	Na2CO3	25
9	Pd(OAc)2	Pn-Bu3HBF4	Na2CO3	<5
10	Pd(OAc)2	Xphos	Na2CO3	<5
11	Pd(OAc)2	SPhos	Na2CO3	<5
12	Pd(OAc)2	PCy3HBF4	NaOAc	44
13	Pd(OAc)2	PCy3HBF4	KOAc	15
14	Pd(OAc)2	PCy3HBF4	K2CO3	36
15	Pd(OAc)2	PCy3HBF4	K3PO4	34
16	Pd(OAc)2	PCy3HBF4	Li2CO3	20
17	Pd(OAc)2	PCy3HBF4	NaOt-Bu	16
18	Pd(CH3CN)2Cl2	PCy3HBF4	Na2CO3	55
19	Pd(PPh3)2Cl2	PCy3HBF4	Na2CO3	52
20	Pd(acac)2	PCy3HBF4	Na2CO3	47
21	Pd(TFA)2	PCy3HBF4	Na2CO3	64
22	Pd(dba)2	PCy3HBF4	Na2CO3	58
23	Pd2(dba)3	PCy3HBF4	Na2CO3	56
24	PEPPSI-IPr	PCy3HBF4	Na2CO3	<5
25c	Pd(TFA)2	PCy3HBF4	Na2CO3	58
26d	Pd(TFA)2	PCy3HBF4	Na2CO3	69
27e	Pd(TFA)2	PCy3HBF4	Na2CO3	60
28f	Pd(TFA)2	PCy3HBF4	Na2CO3	77

^aConditions: amide (1.0 equiv), B₂pin₂ (2.0 equiv), [Pd] (5 mol %), ligand (20 mol %),base (2.0 equiv), dioxane(0.25 M), 150 °C, and 15 h.

^bGC/¹H NMR yields.

^cB₂pin₂ (1.2 equiv).

^dNa₂CO₃ (1.0 equiv).

^eNa₂CO₃ (0.5 equiv).

^fB₂pin₂ (1.2 equiv), Na₂CO₃ (1.0 equiv). See the Supporting Information for details.