Table 1.
Optimization of reaction conditionsa.
 | ||||||
|---|---|---|---|---|---|---|
| Entry | L for Cu | L for Ir | PG | Yield (%)b | drc | ee (%)d |
| 1 | (S,Sp)-L1 | (Sa,S,S)-L5 | CO2Me | 95 | 1:1 | 91 (90) |
| 2 | (S,Sp)-L1 | (Ra,R,R)-L5 | CO2Me | 96 | 1:1 | 93 (97) |
| 3 | (S,Sp)-L1 | rac-L5 | CO2Me | 95 | 1:1 | 88 (89) |
| 4 | rac-L1 | (Sa,S,S)-L5 | CO2Me | 94 | 1.6:1 | 22 (15) |
| 5 | (S,Sp)-L1 | (Sa,R,R)-L6 | CO2Me | 92 | 2:7 | 92 (99) |
| 6 | (S,Sp)-L1 | (Sa,S,S)-L7 | CO2Me | 90 | 1:1 | 98 (98) |
| 7 | (S,Sp)-L1 | (Sa,S,S)-L8 | CO2Me | 94 | 3:2 | 99 (93) |
| 8 | (S,Sp)-L1 | (R,Ra)-L9 | CO2Me | 98 | >20:1 | 99 |
| 9 | (S,Sp)-L1 | (S,Ra)-L10 | CO2Me | 96 | 9:1 | 99 (63) |
| 10 | (S,Sp)-L2 | (R,Ra)-L9 | CO2Me | 95 | 5:1 | 99 (97) |
| 11 | (S,Sp)-L3 | (R,Ra)-L9 | CO2Me | 89 | 10:1 | 99 (89) |
| 12 | (S,Sp)-L4 | (R,Ra)-L9 | CO2Me | 90 | 9:1 | 99 (94) |
| 13 | (S,Sp)-L1 | (R,Ra)-L9 | Ac | n.r. | - | - |
| 14 | (S,Sp)-L1 | (R,Ra)-L9 | Boc | 30 | 12:1 | 99 |
| 15e | - | (R,Ra)-L9 | CO2Me | n.r. | - | - |
| 16f | (S,Sp)-L1 | - | CO2Me | n.r. | - | - |
aAll reactions were carried out with 0.30 mmol of 1a, 0.20 mmol of 2 and 0.40 mmol of DIPEA in 2 mL of CH2Cl2 at room temperature (see Supplementary Methods for the detailed preparation of Cu/L and Ir(I)/L complexes). Cu(I) = Cu(MeCN)4BF4, Ir(I) = [Ir(COD)Cl]2
bYields refer to the isolated products after chromatographic purification
cThe dr value was determined by the crude 1H NMR
dThe ee value was determined by HPLC analysis
eWithout Cu(I)/(S,Sp)-L1
fWithout Ir(I)/(R,Ra)-L9