Table 2.

Synthesis of Saturated 1,4-Benzodiazepines^a

entry	substrate	product	yield (%)b
1	14b	17	78
2	14b	18	88
3	14c	19	94
4	14d	20	71
5	14d	21	74
6	14e	22	82c
7	14a	15	65
8	14a	23	81c
9	14a	24	62
10	14a	25	84
11	14a	26	60

^aConditions: Reactions were conducted on a 0.15 mmol scale using 1.0 equiv substrate, 2.0 equiv ArBr, 2.0 equiv NaO^tBu, 2 mol % PdCl₂(MeCN)₂, 4 mol % PPh₂Cy, xylenes (0.2 M), 135 °C, 18–24 h reaction time.

^bIsolated yield (average of two experiments). In all cases, 2,3-disubstituted products were obtained with >20:1 dr.

^cThis product contained ca. 8% of ketone side product16.