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Synlett 2010(9): 1359-1362  
DOI: 10.1055/s-0029-1219928
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Mitsuru Kitamura*, Kazufumi Shiomi, Daisuke Kitahara, Yasuaki Yamamoto, Tatsuo Okauchi
Department of Applied Chemistry, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu-shi, Fukuoka 804-8550, Japan
Fax: +81(93)8843304; e-Mail: kita@che.kyutech.ac.jp;
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Publication History

Received 11 March 2010
Publication Date:
12 May 2010 (online)

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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).