Table 2.

CuBr-catalyzed regioselective diamination of dienes^a

entry	substrate (1)	product (4)	yield (%)b
1			97 (96:4)c
2			95
3			81
4	1f,R = Ph		92 (97:3)c
5			95
6	1h,n = 2		99
7	1i,n = 3		94
8			85
9			95 (97:3)c,d
10			98
11	1m,R = Ph		96 (89:11)c
12			94
13			90
14			95

^aAll reactions were carried out with olefin 1 (0.20 mmol), di-tert-butyldiaziridinone (2) (0.22 mmol), CuBr (0.010 mmol) in CDCl₃ (0.4 mL) under Ar with vigorous stirring at 0 °C for 20 h unless otherwise stated. For entry 1, 1c (0.19 mmol) was used. For entry 2, olefin 1d (0.25 mmol, E:Z = 15.7:1, E isomer: 0.24 mmol) and 2 (0.2 mmol) were used. For entry 7, the reaction was carried out on 0.40 mmol scale. For entry 9, CuBr (0.020 mmol) was used.

^bIsolated yield based on 1 except for that of entry 2 which was based on 2.

^cThe ratio of 4 to 3 was determined by analysis of ¹H NMR spectrum of the crude reaction mixture.

^dThe stereochemistry was tentatively assigned based upon sterics.