To a solution of LiAIH, (94.9 mg, 2.5 mmol) in THF (5.0 mL) was added a solution of (R)-BINOL (20 mL. 5.0 mmol, 0.25 M in THF) at 0'C. After 30 min stirring at O'C, this solution of I(O.1 M in THF) was directly used for Michael reactions. 7: To a stirred solution of the catalyst I(0.05 mmol) in THF (0.5 mL) was successively added cyclohexenone (6) (48 pL, 0.5 mmol) and dibenzyl malonate (4) (125 pL, 0.5 mmol) at 0°C. After 72 h stirring at room temperature, the reaction mixture was treated with 1 N HCI (2.0 mL) and extracted with EtOAc ( 3 x 10 mL). The combined organic extracts were washed with brine, dried (NaSO,). and concentrated to give an oily residue. Purification by flash chromatography (SO,. 25% acetone/hexane) gave the Michael adduct 7 (172.0 mg, 88% yield) in 99% ee. The spectral and analytical data of 7 were in agreement with those of Ref. [2]. 13: To a solution of cyclopentenone (1) (84 pL, 1 .O mmol), methyl diethylmalonate (2) (138 pL, 1.0 mmol) and 3-phenylpropanal (12) (158 pL, 1.2 mmol) in THF (1.0 mL) was added a solution of the AILi-(R)-BINOL complex I ( l . 0 mL, 0.1 M in T H E 0.1 mmol) at 0°C. After 36 h stirring at room temperature, the reaction was quenched with 1 N HCI at 0°C and worked up as described for 7. The oily residue was purified by flash chromatography (SO,, acetone:hexane 1 :9) to give 13 (250 mg, 0.64 mmol. 64% yield). The optical purity of 13 was determined by HPLC analysis on a chiral phase (DAICEL CHIRALPAK AD, iF'rOH:hexane 1:9).
[z]g4 = + 18.3 (c = 0.66 in chloroform) (91 % ee); 'H NMR (270 MHz, CDCI,):