Table 1.

Optimization of the reaction conditions.^[a]

Entry	Catalyst	Ligand	Additive	Yield 2 a [b]	Yield 3 a
1	Cu(OAc)2	PnBu3	iPr2EtN	45 % (38 %[c])	32 %
2	Cu(OTf)2	PnBu3	iPr2EtN	0 %	2 %
3	CuCl2	PnBu3	iPr2EtN	0 %	0 %
4c	CuCl2	PnBu3	iPr2EtN	42 %	26 %
5[c]	CuCl	PnBu3	iPr2EtN	22 %	34 %
6	CuOAc	PnBu3	iPr2EtN	29 %	20 %
7	Cu(OAc)2	PPh3	iPr2EtN	18 %	40 %
8	Cu(OAc)2	PCy3	iPr2EtN	33 %	23 %
9	Cu(OAc)2	phen	iPr2EtN	trace	8 %
10	Cu(OAc)2	bpy	iPr2EtN	0 %	4 %
11[d]	Cu(OAc)2	PnBu3	iPr2EtN	14 %	39 %
12[e]	Cu(OAc)2	PnBu3	iPr2EtN	31 %	18 %
13	Cu(OAc)2	PnBu3	–	28 % (16 %)	28 %
14	Cu(OAc)2	PnBu3	benzophenone	48 %	22 %
15	Cu(OAc)2	PnBu3	2‐norbornene	59 % (50 %)	16 %
16	Cu(OAc)2	PnBu3	acrylonitrile	69 % (66 %)	12 %
17[f]	Cu(OAc)2	PnBu3	acrylonitrile	78 % (73 %)	11 %
18[f]	Cu(OAc)2	–	acrylonitrile	0 %	0 %
19[f]	–	PnBu3	acrylonitrile	0 %	0 %

[a] Reaction conditions: 1 a (0.2 mmol), B₂pin₂ (0.6 mmol), Cu catalyst (0.02 mmol), ligand (0.04 mmol), and additive (0.2 mmol) in toluene (2 mL) at 80 °C. [b] Yields were determined by GC/MS analysis with n‐dodecane as an internal calibration standard. Yields of isolated products are given in parentheses. [c] 20 mol % KOAc. [d] 60 °C. [e] 90 °C. [f] 4 h.