Table 2.

Generality of the PdL¹_R(OTf)/RuL²_S-matched catalyst system^a

Entry		Product 3	Yield (%)	b/l	syn/anti	erb
1c,d		R = H	82	>95:5	>95:5	>99:1 (R,S)
2		R = Me	99	>95:5	>95:5	>99:1 (R,S)
3e		R = Et	98	>95:5	>95:5	>99:1
4e		R = iPr	91	>95:5	>95:5	>99:1
5 f		R = tBu	<5	n.d.	n.d.	n.d.
6e,f		R = CH2OCH3	96	>95:5	>95:5	>99:1
7e		R = H	97	>95:5	>95:5	99:1
8e		R = p-CH3O	95	>95:5	>95:5	>99:1
9		R = p-Cl	92	>95:5	>95:5	>99:1 (R,S)
10e,g,h		R = Me	91	>95:5	>95:5	>99:1
11i		R = Bn	<5	n.d	n.d	n.d
12e,g,h		R = F	89	>95:5	>95:5	99:1
13e,g,h			97	>95:5	>95:5	>99:1
14		R = o-F	99	>95:5	>95:5	>99:1 (R,S)
15e		R = o-Me	97	>95:5	>95:5	99:1
16e		R = o-CH3O	96	>95:5	>95:5	>99:1
17		R = m-F	99	>95:5	>95:5	>99:1 (R,S)
18e		R = m-Me	98	>95:5	>95:5	>99:1
19e		R = m-CH3O	96	>95:5	>95:5	>99:1
20		R = p-F	99	>95:5	>95:5	99:1 (R,S)
21e		R = p-Cl	97	>95:5	>95:5	>99:1
22e,h,j		R = p-CF3	87	93:7	>95:5	99:1
23e		R = p-Me	98	>95:5	>95:5	99:1
24e		R = p-CH3O	99	>95:5	>95:5	>99:1
25			95	>95:5	>95:5	>99:1 (R,S)
26e,g			97	>95:5	>95:5	>99:1
27 h			93	>95:5	>95:5	>99:1 (R,S)
28			48	<5:95	—	64:36

^aConditions unless otherwise specified: [1] = 500 mM; [2] = 600 mM; [PdL¹_R(OTf)] = [RuL²_S] = 5.00 mM; 1,4-dioxane 1.00 mL; 10 °C; 24 h.

^bEr; enantiomer ratio. Symbols in parentheses are absolute configuration of major stereoisomer. Details on determination are provided in the Supplementary Information.

^c[1] = 500 mM; [2] = 750 mM; [PdL¹_R(OTf)] = 1.25 mM; [RuL²_S] = 2.50 mM.

^dProduct was isolated as a β-hydroxy ester after one pot-reduction using K-selectride.

^eRelative and absolute configurations were not determined. Structures drawn were estimated from the structure-confirmed analogs.

^fReaction time 48 h.

^g[1] = 250 mM; [2] = 500 mM; [PdL¹_R(OTf)] = [RuL²_S] = 2.50 mM.

^hReaction time 72 h.

ⁱ4 mol% of PdL¹_R(OTf) and 4 mol% of RuL²_S were used.

^j2 mol% of PdL¹_R(OTf) and 4 mol% of RuL²_S were used.