Pinacol Coupling of 2,2′-Biaryldiketone: An Application for the Synthesis of Enantiopure 3,4-Dihydrodibenzo[c,g]phenanthrene-3,4-diol Derivatives

Abstract

Pinacol coupling of 2,2′-biaryldiketone gave trans-diol selectively. In the reaction of axially chiral diketones, enantiomerically pure diols were obtained. Various enantiopure 3,4-dihydro­dibenzo[c,g]phenanthrene-3,4-diol could be synthesized by the pinacol coupling of optically active 2,2′-diacyl-1,1′-binaphthalene derived from (P)-1,1′-bi-2-naphthol [(S)-BINOL].

Key words

biaryls - diastereoselective reactions - diols - optically active compounds - pinacol coupling

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10

CCDC 768807 contains the supplementary crystallographic data for compound 2.

14

Compound 7a and the enantiomer of 7a derived from (M)-BINOL proved to have an ee value of greater than 99% by HPLC with chiral column (DAICEL OD-H).

15

CCDC 623903 contains the supplementary crystallographic data for compound 7a.

17

Typical Procedure is Described for the Synthesis of 7d To a solution of diketone (P)-6d (415 mg, 0.897 mmol) in THF (7 mL) was added 1 M TiCl₄ in CH₂Cl₂ (2 mL) and Zn (0.260 g, 3.98 mmol) at -10 ˚C. After stirring for 6 h at -10 ˚C, the reaction was quenched by adding 10 wt% K₂CO₃ solution. The mixture was filtered through a Celite pad (washed with EtOAc). The resulting mixture was extracted with EtOAc three times. The combined organic extracts were washed with brine, dried over Na₂SO₄, and concentrated in vacuo. The residue was purified by flash column chromatography (hexane-EtOAc = 8:2) to afford the diol 7d (239 mg, 69% yield, >99% ee) and acetal 8d (62 mg, 18% yield).