Table 1.

Scope of Electron-deficient Heterocycles in Hydrosilylation - Dehydrogenative Cyclization^a

entry	intermediate	2, yieldb	product	3, yieldb
1	2a: R = H	84%	3a: R = H	83%
2c	2a: R = H	83%	3a: R = H	74–82%
3	2b: R = Me	86%	3b: R = Me	87%
4	2c: R = F	86%	3c: R = F	68% (5:1)
5	2d: R = Cl	61%	3d: R = Cl	64%
6	2e	95%	3e	traces
7	2f: R = H	93%	3f: R = H	79%
8	2g: R = Me	90%	3g: R = Me	86%
9	2h: R = Cl	83%	3h: R = Cl	75%
10	2i: R1 = H, R2 = H	dec.	3i: R1 = H, R2 = H	N/A
11	2j: R1 = Me, R2 = H	48%1	3j: R1 = Me, R2 = H	36%
12	2k: R1 = Me, R2 = F	76%d	3k: R1 = Me, R2 = F	73%
13	2l: R1 = OMe, R2 = H	67%	3l: R1 = OMe, R2 = H	72%
14	2m: R1 = CF3, R2 = H	76%	3m: R1 = CF3, R2 = H	77%
15	2n	97%	3n	74%
16	2o	96%	3o	78%
17	2p	90%	3p	74%e
18	2q	94%	3q	56%e

^aHydrosilylation reaction conditions: 1 (1.0 mmol), H₂SiPh₂ (1.02 mmol), Ni(cod)₂ (5 mol %), PPh₃ (20 mol %), and THF (1.0 mL) were stirred at 90 °C for 2 h under nitrogen. Dehydrogenative coupling reaction conditions: 2 (0.5 mmol), [Ir(cod)OMe]₂ (2 mol %) and 1,10-phenantroline (4 mol %), norbornene (1,2 equiv), and THF (1.0 mL) were stirred at 100 °C for 12 h under nitrogen.

^bIsolated yield.

^cReaction was performed on 10 mmol scale using 2.5 mol % Ni-catalyst and 0.25–0.5 mol % Ir-catalyst.

^d10 mol % Ni(cod)₂ was used.

^e48 h at 100 °C.