Table 4.

Selective Amination of Homoallylic Carbamates

entry	substrate	catalysta,b,c		7	8	dr (cis:trans)
1	6a	Rh2(OAc)4		58% 7a	18% 8a	(100:0)
		1:1.25 AgOTf:phen		67% 7a	4% 8a	---
		1:3 AgOTf:phen		0% 7a	93% 8a	---
2	6b	Rh2(esp)2		45% 7b	25% 8bd	nd
		1:1.25 AgOTf:phen		89% 7b	9% 8b	3.2:1
		1:3 AgOTf:phen		4% 7a	87% 8b	3:1
3	6c	Rh2(OAc)4		68% 7c	14% 8c	(0:100)
		1:1.25 AgOTf:phen		88% 7c	3% 8c	---
		1:3 AgOTf:phen		11% 7c	73% 8c	---
4	6d	Rh2(OAc)4		35% 7d	5% 8d	---
		1:1.25 AgOTf:phen		85% 7d	<1% 8d	---
		1:3 AgOTf:phen		23% 7d	66% 8d	---
5	6e	Rh2(esp)2		25% 7e	21% 8ed	nd
		1:1.25 AgOTf:phen		54% 7e	39% 8ed	nd
		1:3 AgOTf:phen		0% 7e	68% 8e	2.4:1

^aRh cat.: 3 mol %, 2 equiv PhIO, 4 Å MS, CH₂Cl₂.

^bAziridination: 20 mol % AgOTf, 25 mol % phen, 2 equiv PhlO, 4 Å MS, CH₂Cl₂.

^cC–H insertion: 10 mol % AgOTf, 30 mol % phen, 3.5 equiv PhlO, 4 Å MS, CH₂Cl₂.

^dNMR yields with mesitylene as the internal standard.