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LETTER
Ed. 2001, 40, 92. (d) Whitesell, J. K. Chem. Rev. 1989, 89,
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tries 8–11). The 2-fluorophenyl ketone 6l gave only the
diol 9l in 72% yield (entry 12).
In conclusion, we found that the pinacol coupling of enan-
tiomerically pure axially chiral 2,2¢-biaryldiketones pro-
ceeds to give trans-diols in the enantiomerically pure
form. By this method, various enantiopure 3,4-dihydro-
dibenzo[c,g]phenanthrene-3,4-diols could be synthesized.
Currently asymmetric reactions using the diol 6 are under
investigation.
(5) (a) Fobbe, H.; Neumann, W. P. J. Organomet. Chem. 1986,
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34, 335.
(9) Mukaiyama, T.; Sato, T.; Hanna, J. Chem. Lett. 1973, 1041.
(10) CCDC 768807 contains the supplementary crystallographic
data for compound 2.
(11) (a) Ohta, T.; Ito, M.; Inagaki, K.; Takaya, H. Tetrahedron
Lett. 1993, 34, 1615. (b) Kurz, L.; Lee, G.; Morgans, D.;
Waldyke, M. J.; Ward, T. Tetrahedron Lett. 1990, 31, 6321.
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Chem. Jpn. 2003, 61, 1056. (b) Ishii, Y.; Sakaguchi, S.;
Iwahama, T. Adv. Synth. Catal. 2001, 343, 393.
(13) Silvestre, S. M.; Salvador, J. A. R. Tetrahedron 2007, 63,
2439.
(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.
(16) Hall, D. M.; Turner, E. E. J. Chem. Soc. 1955, 1242.
(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).
Acknowledgment
This research was partially supported by a Grant-in-Aid for Scien-
tific Research from the Ministry of Education, Science, Sports and
Culture. We thank Dr. T. Moriguchi (Department of Applied Che-
mistry, Kyushu Institute of Technology) and Dr. T. Matsumoto
(Institute for Materials Chemistry and Engineering, Kyushu Uni-
versity) for assistance in X-ray crystallographic analysis.
References and Notes
(1) Ohmori, K.; Kitamura, M.; Suzuki, K. Angew. Chem. Int.
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Synlett 2010, No. 9, 1359–1362 © Thieme Stuttgart · New York