Direct One-Pot Synthesis of 2,3-Diarylbuta-1,3-diene via Self-Coupling of Acetophenones

Abstract

A mild and straightforward route to 2,3-diarylbuta-1,3-diene is described here. By treatment with SmI₂-Ac₂O, acetophenone and its analogues underwent self-coupling reactions and subsequent elimination to give a series of 2,3-diarylbuta-1,3-dienes in moderate to good yields.

Key words

2,3-diarylbuta-1,3-diene - self-coupling - acetophenone

References and Notes

• 1a Boehrner J. Grigg R. Tetrahedron  1999,  55:  13463 
• 1b Shimizu H. Hatano T. Matsuda T. Iwamura T. Tetrahedron Lett.  1999,  40:  1505 
• 1c Ikeda Z. Oshima K. Matsubara S. Org. Lett.  2005,  7:  4859 
• 1d Abu-Yousef IA. Harpp DN. J. Org. Chem.  1997,  62:  8366 
• 1e Paik IH. Xie S. Shapiro TO. Labonte T. Sarjeant AAN. Baege AC. Posner GH. J. Med. Chem.  2006,  49:  2731 
• 1f Takahashi T. Xi Z. Fischer R. Huo S. Xi C. Nakajima K. J. Am. Chem. Soc.  1997,  119:  4561 
• 1g Dell CP. J. Chem. Soc., Perkin Trans. 1  1998,  3867 
• 2 Lee PH. Seomoon D. Lee K. Org. Lett.  2005,  7:  343 
• 3 Bohmer J. Grigg R. Tetrahedron  1999,  55:  13463 
• 4a Dodson RM. Srinivasan V. Sharma KS. Sauers RF. J. Org. Chem.  1972,  37:  2367 
• 4b Baldwin JE. Lusch MJ. J. Org. Chem.  1979,  44:  1923 
• 4c Johlin JM. J. Am. Chem. Soc.  1917,  39:  292 
• 4d Iwai I. Ide J. Org. Synth., Coll. Vol. VI   Wiley; New York: 1988.  p.531 
• 4e Alder K. Haydn J. Justus Liebigs Ann. Chem.  1950,  570:  201 
• 4f Wagner RA. Brinker UH. Synthesis  2001,  376 
• 5 Ishino Y. Nishiguchi I. Takihira F. Hirashima T. Tetrahedron Lett.  1980,  21:  1527 
• 6a McMurry JE. Felming MP. J. Am. Chem. Soc.  1974,  96:  4708 
• 6b Mukaiyama T. Sato T. Hanna J. Chem. Lett.  1973,  2:  1041 
• 6c Fürstner A. Bogdanovic B. Angew. Chem. Int. Ed.  1996,  35:  2442 
• 6d McMurry JE. Chem. Rev.  1989,  89:  1513 
• 6e Lenoir D. Synthesis  1989,  883 
• 6f Duan XF. Zeng J. Lu JW. Zhang ZB. J. Org. Chem.  2006,  71:  9873 
• 7 Addie MS. Taylor RJK. ARKIVOC  2000,  (v):  660 
• 8a Li J. Xu XX. Zhang YM. Tetrahedron Lett.  2003,  44:  9349 
• 8b Li J. Wang XX. Zhang YM. Tetrahedron  2004,  60:  5793 
• 9a Namy JL. Kagan HB. Tetrahedron Lett.  1983,  24:  765 
• 9b Molander GA. Etter JB. Harring LS. Thorel PJ. J. Am. Chem. Soc.  1991,  113:  8036 
• 9c Fuchs JR. Mitchell ML. Shabangi M. Flowers RA. Tetrahedron Lett.  1997,  38:  8157 
• 9d Chiara JL. Cabri W. Hanessian S. Tetrahedron Lett.  1991,  32:  1125 
• 9e Uenishi J. Masuda S. Wakabayashi S. Tetrahedron Lett.  1991,  32:  5097 

10

General Procedure for the Synthesis of 2,3-Diarylbuta-1,3-dienes (Method A): To the stirred acetophenone or its analogues 1 (1 mmol) in an oven-dried glassware under a nitrogen atmosphere, samarium diiodide (1 mmol) in THF (15 mL) was added dropwise. Generally the reaction finished within 15 min. After the deep blue color faded, Ac₂O (1.2 mmol) was added to the yellow mixture rapidly. The reaction mixture was stirred under reflux until reaction completion. After the usual workup, the crude product was purified by silica gel column chromatography using EtOAc-PE (1:20) as eluent to afford the corresponding pure buta-1,3-diene 2.
General Procedure for the Synthesis of 2,3-Bis(4-bromophenyl)buta-1,3-diene and 2,3-Bis(4-chloro-phenyl)buta-1,3-diene (Method B): To the stirred 4-chloro- or 4-bromo-substituted acetophenone (1 mmol) in an oven-dried glassware under a nitrogen atmosphere, samarium diiodide (1 mmol) in THF (15 mL) was added dropwise. Generally the reaction finished within 15 min. After the deep blue color faded, THF was removed under reduced pressure, then MeCN (3 mL) and Ac₂O (3.0 mmol) were added to the yellow mixture successively, and the resulting mixture was stirred under reflux until reaction completion. After the usual workup, the crude product was purified by silica gel column chromatography using EtOAc-PE (1:20) as eluent to afford the corresponding diene.