Table 1. Optimization studies of enantiodivergent hydroamination of an alkyne.

Reaction conditions: Reactions were carried out using alkyne 1a (0.05 mmol), 2a (1.2 equiv), chiral Rh(III) catalyst (4 mol %), silver carboxylate (2 equiv), and carboxylic acid (2 equiv) at 0°C in a solvent (1 ml) for 12 hours under N₂. Bold font is used to emphasize the reaction standard condition, corresponding to the conditions in Fig. 2. DCM, dichloromethane; HFIP, hexafluoroisopropanol.

Entry	Rh cat.	R (acid)	Solvent	Yield (%)*	ee (%)†
1	Rh1	Me	DCE	47	8
2	Rh2	Me	DCE	50	5
3	Rh3	Me	DCE	23	7
4	Rh4	Me	DCE	<5	–
5	Rh1	tBu	DCE	58	70
6	Rh1	Ad	DCE	58	84
7	Rh1	Ad	DCM	46	76
8	Rh1	Ad	CHCl3	40	75
9	Rh1	Ad	PhCl	28	70
10	Rh1	Ad	TFE	66	81
11	Rh1	Ad	HFIP	48	66
12	Rh2	Ad	TFE	74	89
13‡	Rh2	Ad	TFE	48	90
14	Rh1	Ph	DCE	54	30
15	Rh1	Mes	DCE	62	−91
16‡	Rh1	Mes	DCE	47	−91
17	Rh1	Mes	DCM	60	−90
18	Rh1	Mes	CHCl3	55	−86

*Isolated yields.

†The ee was determined by high-performance liquid chromatography analysis.

‡At −20°C.