Zn(salen)-Catalyzed Enantioselective Phenyl Transfer to Aldehydes and Ketones with Organozinc Reagent

Abstract

A chiral zinc complex of salen was found to be an efficient catalyst for the phenyl transfer of organozinc reagent to aromatic aldehydes and ketones. High enantioselectivities were obtained in reactions of both aromatic aldehydes and ketones (up to 97% and 92% ee, respectively).

Key words

Zn(salen) complex - asymmetric catalysis - phenyl transfer - aldehydes - ketones - diarylmethanol

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• 19 Typical Experimental Procedure is Exemplified by Enantio­selective Phenyl Transfer to p-Chlorobenzaldehyde Diphenylzinc (43.9 mg, 0.2 mmol) was placed in a flask under nitrogen, and diethylzinc (0.38 mL, 1.06 mol·dm^–3 in hexane) was added at r.t. and stirred for 30 min at the temperature. This suspension was added to a solution of salen 1 (10.9 mg, 0.02 mmol) in toluene (0.25 mL) and further stirred at the temperature for 30 min. After the mixture was cooled to –40 °C, p-chlorobenzaldehyde (28.1 mg, 0.2 mmol) was added. After being stirred for 1 h at the same temperature, the mixture was quenched with sat. aq NH₄Cl, allowed to warm to r.t., and extracted with Et₂O and then washed with sat. aq NaCl. The organic extract was dried over anhydrous Na₂SO₄ and concentrated. Silica gel chromatography of the residue (hexane–EtOAc, 19:1 to 9:1) gave the desired product (41.4 mg, 95%) as an oil. The ee of the product was determined to be 94% by HPLC using chiral stationary-phase column as described in the footnote b of Table 1. [α]_D ¹³ +20.2 (c 0.45, CHCl₃) [lit.^10d [α]_D ²³ +19.1 (c 0.83, CHCl₃) for 83% ee, (S)]. All spectral data of products in Tables 1–3 were in accordance with those reported in the literature. Specific Rotation of some Compounds (R)-Cyclohexylphenylmethanol [α]_D ²⁶ +33.9 (c 0.2, CHCl₃) for 76% ee [lit.^10d [α]_D ²³ +38.0 (c 0.4, CHCl₃) for 96% ee, (R)]. (S)-1-(4-Chlorophenyl)-1-phenylethanol [α]_D ¹³ +13.2 (c 0.2, CHCl₃) for 92% ee [lit.^15b [α]_D ²² +14.8 (c 6.5, CHCl₃) for 98% ee, (S)]. (S)-Phenylindan-1-ol [α]_D ¹⁷ +36.9 (c 1.6, CHCl₃) for 88% ee [lit.^15b [α]_D ²⁴ –33.3 (c 1.05, CHCl₃) for 88% ee, (R)]. (S)-1-Cyclohexyl-1-phenylethanol [α]_D ¹³ –7.1 (c 0.75, CH₂Cl₂) for 44% ee [lit.^15a [α]_D ²⁴ +17.9 (c 3.4, CH₂Cl₂) for 99% ee, (R)].