Optimization of enantioselective electrocatalysis.

Entry	1a/1b	Catalyst	Additive	Yield/%
1a	1a	PdCl2	Ligand 1	Trace
2b	1a	PdCl2	Ligand 2	Trace
3c	1a	[Rh]-1	(BzO)2	Trace
4d	1b	[Rh]-2	AdCO2H	67%
5e	1b	[Rh]-1	(BzO)2	57%/93:7 er

^aReaction conditions: 1a (0.8 mmol, 2.0 equiv.), 2a (0.4 mmol), PdCl₂ (10 mol%), ligand 1 (20 mol%), NMe₄Cl (1.0 equiv.), DMF (4.0 mL) at 100 °C, 16 h, under air.

^bReaction conditions: 1a (0.8 mmol, 2.0 equiv.), 2a (0.4 mmol), PdCl₂ (10 mol%), ligand 2 (20 mol%), NMe₄Cl (1.0 equiv.), DMF (4.0 mL) at 100 °C, 16 h, under air.

^cReaction conditions: 1a (0.8 mmol, 2.0 equiv.), 2a (0.4 mmol), [Rh]-1 (5.0 mol%), (BzO)₂ (5.0 mol%), n-Bu₄NOAc (1.0 equiv.), 1,4-dioxane/H₂O (3 : 1) (4.0 mL) at 100 °C, 16 h, under air.

^dReaction conditions: 1b (1.5 equiv., 0.3 mmol), 2a (0.2 mmol), [Rh]-2 (2.5 mol%), KOAc (2.0 equiv.), AdCO₂H (10 mol%), MeOH (4.0 mL), at 35 °C, 6 h, under air.

^eReaction conditions: 1b (1.5 equiv., 0.15 mmol), 2a (0.1 mmol), [Rh]-1 (10 mol%), (BzO)₂ (10 mol%), n-Bu₄NPF₆ (3.0 equiv.), MeOH (4.0 mL), at 35 °C, 6 h, under air.