1-Naphthaldehyde → Butanedione

Participants

Reaction Steps

10 g of toluene, 1 mmol of a zinc compound such as diethylzinc (Examples 1 to 6 and 9), phenylzinc hydride (Example 7) or zinc hydride (Example 8), and 1 mmol of one of the ligands of the secondary diimine type shown in Table 1 overleaf were added to a 100 ml three-necked flask. The mixture was stirred for 10 min at 20° C., following which 12 g (100 mmol) of acetophenone were added. 6.5 g (100 mmol) of PMHS were then added over a period of 10 minutes, and the solution was stirred continuously for 8 h at 20° C. The complete disappearance of the acetophenone was traced by chromatography. The reaction solution was slowly poured onto an aqueous 30% soda solution (0.15 mol of NaOH). The aqueous phase was decanted, the toluene was evaporated from the organic solution, and the alcohol produced was vacuum-distilled. The enantiomeric excess of the product was determined by chromatographic analysis in the gaseous phase on a chiral column of the Chirasil® type. The Schiff base diimine ligands were prepared by reacting 1 equivalent of commercially available (1R,2R)-(−)diaminocyclohexane with 2 equivalents of 1-naphthaldehyde (Example 1), heliotropin (Example 2), mesitylaldehyde (Example 3) and 2-formylpinane (Example 4) in accordance with Krasik and Alper's description, Tetrahedron, 1994, 50, 4347. The diimine ligands of Examples 5 to 8 were obtained by condensing 2 equivalents of (R)-α-naphthylethylamine (Example 5) or (R)-(α)-phenylethylamine with 1 equivalent of 2,3-butanedione in accordance with Dieck and Dietrich's description, Chem. Ber., 1984, 117, 694. The pyridinyl-imine ligand of Example 9 was prepared by condensing 2-pyridyl carboxaldehyde and (R)-α-phenylethylamine in accordance with Brunner, Reiter and Riepel's method, Chem. Ber., 1984, 117, 1130.

Provenance & Evidence