Table 2.

Scope of Rh-Catalyzed Hydroamination of Primary Amines^a

entry	mol % [Rh]		aminoalkene	product	time (h)	yieldb (dr)c	ratio (amine:imine)c
1	3				15	66% (dr = 1.3:1)	9:1
2d	4				7	a; n=1; 76%e	>95:5
3d	4				8	b; n=2; 77%	>95:5
4f,g	18				15	40%	>95:5
5f,h	3				14	64%i	7:1
6j	3		a; R=OTBDPS		18	71% (dr = 1.6:1)	>95:5
7	3		b; R=4-(CO2Me)C6H4		21	64% (dr = 1.6:1)	10:1
8	5		c; R=4-(CH2CN)C6H4		12	79% (dr = 1.5:1)	>95:5
9	5		d; R=4-(CH3(O)C)C6H4		16	61% (dr = 1.5:1)	10:1
10	5		e; R=4-(CH2OH)C6H4		8	56%k (dr = 1.1:1)	7:1
11	1		a; R = H	a; R = H	5	87%	>95:5
12	2		b; R = Cl	b; R = Cl	6	84%	>95:5
13	1				7	74% dr = (1.1:1)	>95:5

^aReaction conditions: 0.5 mmol aminoalkene, [Rh(CH₃CN)₂COD]BF₄ (1-18 mol %), and L1 (1.2-19 mol %) in 1 mL of tBuOH at 70 °C for unless otherwise specified.

^bIsolated yield.

^cRatio determned by ¹H NMR spectroscopy.

^dProduct isolated as Boc carbamate.

^eNMR yield; the product was isolated in 67% yield as an 10:1:1 mixture of 7a-Boc:BocNEt₂:N-Boc-1-amino-3-pentene

^fReaction run at 100 °C in dioxane.

^g3.3:1 mixutre of E:Z isomers.

^h10:1 mixture of E:Z isomers.

ⁱIsolated as a 1.8:1 mixture of olefin isomers (internal:terminal).

^jReaction run on a 0.25 mmol scale.

^kIsolated as a 97:3 mixture of alcohol:aldehyde products.