A Double Suzuki Approach for Synthesis of Substituted Diarylmethylidenefluorenes

Abstract

A convenient synthesis of substituted diarylmethylidenefluorene derivatives, using a double Suzuki reaction, is reported.

Key words

diarylmethylidenefluorene - dibromomethylidenefluorene - Suzuki reaction - arylboronic acids - Pd-mediated coupling

References and Notes

• 1 Onikubo S, Yauchi H, Yagi T, Kaneko T, Tanaka H, and Takada Y. inventors; JP  2004206893.  ; Chem. Abstr. 2004, 141, 131068
• 2 Heeney M. Bailey C. Giles M. Shkunov M. Sparrowe D. Tierny S. Zhang W. McCulloch I. Macromolecules  2004,  37:  5250 
• 3a Mills NS. Tirla C. Benish MA. Rakowitz AJ. Bebell LM. Hurd CMM. Bria ALM. J. Org. Chem.  2005,  70:  10709 
• 3b Mills NS. Benish MA. Ybarra C. J. Org. Chem.  2002,  67:  2003 
• 3c Mladenova G. Chen L. Rodriquez CF. Siu KWM. Johnston LJ. Hopkinson AC. Lee-Ruff E. J. Org. Chem.  2001,  66:  1109 
• 3d Mills NS. Malinky T. Malandra JL. Burns EE. Crossno P. J. Org. Chem.  1999,  64:  511 
• 3e Mills NS. Malandra JL. Hensen A. Lowery JA. Polycycl. Arom. Comp.  1997,  12:  239 
• 4 Luisa M. Franco MB. Herold BJ. J. Chem. Soc., Perkin Trans. 2  1988,  443 ; and references cited there in
• 5 Murphy WS. Hauser CR. J. Org. Chem.  1966,  31:  85 
• 6 Schönberg A. Fateen A. Sammour A. J. Am. Chem. Soc.  1957,  79:  6020 
• 7 Johnson AW. LaCount RB. Tetrahedron  1960,  9:  130 
• 8 Rodi AK. Anseime G. Ranaivonjatovo H. Eseudi J. Chem. Heterocycl. Comp. (Engl. Transl.)  1999,  35:  965 
• 9a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 9b Suzuki A. J. Organomet. Chem.  1999,  576:  147 
• 9c Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
• 10a Soderquist JA. Leon G. Colberg JC. Martinez I. Tetrahedron Lett.  1995,  36:  3119 
• 10b Shen W. Synlett  2000,  737 
• 10c Bauer A. Miller MW. Vice SF. McCombie SW. Synlett  2001,  254 
• 10d Oh CH. Lim YM. Bull. Korean Chem. Soc.  2002,  23:  663 
• 10e Barluenga J. Moriel P. Aznar F. Valdès C. Adv. Synth. Catal.  2006,  348:  347 
• 11a Neidlein R. Winter M. Synthesis  1998,  1362 
• 11b Ramirez F. Desai NB. McKelvie N. J. Am. Chem. Soc.  1962,  84:  1745 
• 11c Corey EJ. Fuchs PL. Tetrahedron Lett.  1972,  13:  3769 

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Selected Experimental Procedure: Under an argon atmosphere, a solution of dibromide 2 (200 mg, 0.6 mmol) in benzene (15 mL) was treated with solid Na₂CO₃ (154 mg, 1.5 mmol), Pd(PPh₃)₂Cl₂ (40 mg, 0.06 mmol) and boronic acid 3h (145 mg, 0.9 mmol) and the contents were degassed for 5 min. To this, EtOH (0.5 mL) and H₂O (0.5 mL) were added and the reaction mixture was heated at 80 °C for 10 h. The reaction mixture was cooled, the catalyst (40 mg, 0.06 mmol) and boronic acid 3h (145 mg, 0.9 mmol) were introduced and the heating at 80 °C was continued for an additional 10 h. In general, the reactions are light-sensitive and covering the reaction vessel with aluminum foil is recommended. The reaction mixture was concentrated under reduced pressure and diluted with EtOAc (30 mL) and washed with H₂O. The organic layer was separated, dried (Na₂SO₄), concentrated and purified by silica gel column chromatography (10% EtOAc-PE). Recrystallization from toluene gave 1h (217 mg, 88%) as yellow colored crystals suitable for single-crystal X-ray diffraction studies. [13]
Spectral Data of Compound 1h: mp 231-233 °C (toluene). IR (CHCl₃): 3019, 1682, 1601, 1446, 1403, 1360, 1266, 1215, 1075, 958, 849 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.65 (s, 6 H), 6.61 (br dt, J = 0.83, 8.0 Hz, 2 H), 6.92 (dt, J = 1.2, 7.4, 8.0 Hz, 2 H), 7.26 (dt, J = 1.0, 7.4 Hz, 2 H), 7.48 (br dt, J = 1.6, 8.1 Hz, 4 H), 7.65-7.74 (m, 2 H), 8.64 (br dt, J = 1.8, 8.1 Hz, 4 H). ¹³C NMR (50 MHz, CDCl₃): δ = 26.6 (q), 119.4 (d), 124.8 (d), 126.6 (d), 128.4 (d), 128.9 (d), 129.9 (d), 135.7 (s), 136.6 (s), 137.8 (s), 140.7 (s), 141.9 (s), 146.9 (s), 197.5 (s). Anal. Calcd for C₃₀H₂₂O₂: C, 86.93; H, 5.35. Found: C, 86.97; H, 5.59.

13

The crystallographic data for 1h has been deposited with the Cambridge Crystallographic Data Centre with deposition no. CCDC 625077. Copies of the data can be obtained free of charge on application to the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: [phone]; e-mail: [e-mail]].