Table 1. Optimization of the Reaction Conditionsa.
entry | R1 | R2 | cat. | solvent | yieldb | e.r.c |
---|---|---|---|---|---|---|
1 | Bn | Bn | A | CH2Cl2 | traces | – |
2 | Me | Bn | A | CH2Cl2 | traces | – |
3 | Me | Bzh | A | CH2Cl2 | 14% | 55:45 |
4 | Me | Bzh | B | CH2Cl2 | 20% | 55:45 |
5 | Me | Bzh | C | CH2Cl2 | 20% | 75:25 |
6 | Me | Bzh | D | CH2Cl2 | 45% | 74:26 |
7 | Me | Bzh | D | CHCl3 | 56% | 67:33 |
8 | Me | Bzh | D | 1,2-DFB | 47% | 79:21 |
9 | Me | Bzh | D | 1,2-DCE | 51% | 81:19 |
10 | Et | Bzh | D | 1,2-DCE | 40% | 96:4 |
11d,e | Et | Bzh | D | 1,2-DCE | 93% | 96:4 |
12 | Bn | Bzh | D | 1,2-DCE | >95% | 96:4 |
13d,f | Bn | Bzh | D | 1,2-DCE | 98% | 96:4 |
Reaction conditions: 0.05 mmol of 1, 0.25 M, 10 mol% cat., stirring at 900 rpm, 24 h.
Determined by 19F NMR spectroscopy with 4-fluoroanisole as an internal standard.
Enantiomeric ratios were determined by HPLC using a chiral stationary phase.
Yield of isolated product.
72 h, 10 mol% cat.
48 h, 5 mol% cat.