Table 4. Effect of α-substituent on coumarins in enantioselective allylic alkylation a .
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Entry | X | t [h] | 3 | Yield b [%] | er c |
1 | CN (1a) | 36 | 3aa | 86 | 98 : 2 |
2 | CONH2 (1i) | 36 | 3ia | 81 | 98 : 2 |
3 | CO2Et (1j) | 48 | 3ja | 80 | 97.5 : 2.5 |
4 | CO2Bn (1k) | 48 | 3ka | 85 | 98 : 2 |
5 | CO2H (1l) | 42 | 3la | <5 d | — |
6 | H (1m) | 48 | 3ma | <5 | — |
aReaction conditions: 3 mol% [Ir(COD)Cl]2, 6 mol% L1, 0.24 mmol of 1, 0.2 mmol of 2a and 0.2 mmol of DABCO in 0.6 mL CH2Cl2. The catalyst was prepared via n-PrNH2 activation.
bYields correspond to the isolated product after chromatographic purification.
cer was determined by HPLC analysis on a chiral stationary phase.
d 1m was isolated in 52% yield.