A Highly Efficient Synthesis of 2,5-Disubstituted Furans from Enyne Acetates Catalyzed by Lewis Acid and Palladium

Abstract

A highly efficient synthesis of a wide range of 2,5-disubstituted furans from enyne acetates is described. The reactions are conducted by using Lewis acid and palladium catalyst and provide symmetrical and unsymmetrical products in good to excellent yields, with broad substrate scope, including a variety of aromatic and aliphatic substituents in the 2- and 5-position of the furan ring.

Key words

furan - enyne acetate - Lewis acid - palladium - synthesis

• References and Notes

• 1a Hou XL, Cheung HY, Hon TY, Kwan PL, Lo TH, Tong SY, Wong HN. C. Tetrahedron 1998; 54: 1955
• 1b Donohoe TJ, Ironmonger A, Kershaw NM. Angew. Chem. Int. Ed. 2008; 47: 7314
• 1c Kirsch SF. Org. Biomol. Chem. 2006; 4: 2076
• 2a Gulevich AV, Dudnik AS, Chernyak N, Gevorgyan V. Chem. Rev. 2013; 113: 3084
• 2b Brown RC. D. Angew. Chem. Int. Ed. 2005; 44: 850
• 2c Keay BA. Chem. Soc. Rev. 1999; 28: 209
• 2d Jeevanandam A, Ghule A, Ling YC. Curr. Org. Chem. 2002; 6: 841
• 3 For the Paal–Knorr synthesis, see: Minetto G, Raveglia LF, Sega A, Taddei M. Eur. J. Org. Chem. 2005; 5277 ; and references cited therein

For selected recent examples, see:
• 4a Dudnik AS, Sromek AW, Rubina M, Kim JT, Kel’in AV, Gevorgyan V. J. Am. Chem. Soc. 2008; 130: 1440
• 4b Yao T, Zhang X, Larock RC. J. Am. Chem. Soc. 2004; 126: 11164
• 4c Sniady A, Durham A, Morreale MS, Wheeler KA, Dembinski R. Org. Lett. 2007; 9: 1175
• 4d Xiao Y, Zhang J. Angew. Chem. Int. Ed. 2008; 47: 1903
• 4e Sromek AW, Kel’in AV, Gevorgyan V. Angew. Chem. Int. Ed. 2004; 43: 2280
• 4f Umland K.-D, Palisse A, Haug TT, Kirsch SF. Angew. Chem. Int. Ed. 2011; 50: 9965
• 4g Zhang J, Schmalz H.-G. Angew. Chem. Int. Ed. 2006; 45: 6704
• 4h Liu F, Qian D, Li L, Zhao X, Zhang J. Angew. Chem. Int. Ed. 2010; 49: 6669
• 4i Liu R, Zhang J. Chem. Asian J. 2012; 7: 294
• 4j Gao H, Wu X, Zhang J. Chem. Eur. J. 2011; 17: 2838

For selected recent examples, see:
• 5a Schwier T, Sromek AW, Yap DM. L, Chernyak D, Gevorgyan V. J. Am. Chem. Soc. 2007; 129: 9868
• 5b Dudnik AS, Xia Y, Li Y, Gevorgyan V. J. Am. Chem. Soc. 2010; 132: 7645
• 5c Sromek AW, Rubina M, Gevorgyan V. J. Am. Chem. Soc. 2005; 127: 10500
• 5d Dudnik AS, Gevorgyan V. Angew. Chem. Int. Ed. 2007; 46: 5195
• 5e Li Y, Brand JP, Waser J. Angew. Chem. Int. Ed. 2013; 52: 6743
• 5f Peng L, Zhang X, Ma M, Wang J. Angew. Chem. Int. Ed. 2007; 46: 1905
• 5g Ma S, Yu Z. Angew. Chem. Int. Ed. 2002; 41: 1775
• 6a Rubin M, Rubina M, Gevorgyan V. Chem. Rev. 2007; 107: 3117
• 6b Ma S, Zhang J. J. Am. Chem. Soc. 2003; 125: 12386
• 7a Ma S, Lu L, Zhang J. J. Am. Chem. Soc. 2004; 126: 9645
• 7b Zhang G, Huang X, Li G, Zhang L. J. Am. Chem. Soc. 2008; 130: 1814
• 7c Ma S, Zhang J. Angew. Chem. Int. Ed. 2003; 42: 183

For selected recent examples, see:
• 8a Nishibayashi Y, Yoshikawa M, Inada Y, Milton MD, Hidai M, Uemura S. Angew. Chem. Int. Ed. 2003; 42: 2681
• 8b Lenden P, Entwistle DA, Willis MC. Angew. Chem. Int. Ed. 2011; 50: 10657
• 8c Gabriele B, Mancuso R, Maltese V, Veltri L, Salerno G. J. Org. Chem. 2012; 77: 8657
• 8d Gabriele B, Veltri L, Plastina P, Mancuso R, Vetere MV, Maltese V. J. Org. Chem. 2013; 78: 4919
• 8e Gabriele B, Salerno G, Lauria E. J. Org. Chem. 1999; 64: 7687
• 8f Wang T, Chen X, Chen L, Zhan Z. Org. Lett. 2011; 13: 3324

For selected recent examples, see:
• 9a Shu X.-Z, Liu X.-Y, Xiao H.-Q, Ji K.-G, Guo L.-N, Qi C.-Z, Liang Y.-M. Adv. Synth. Catal. 2007; 349: 2493
• 9b Blanc A, Tenbrink K, Wiebel J.-M, Pale P. J. Org. Chem. 2009; 74: 4360
• 9c Hashmi AS. K, Sinha P. Adv. Synth. Catal. 2004; 346: 432

For selected recent examples, see:
• 10a Suhre MH, Reif M, Kirsch SF. Org. Lett. 2005; 7: 3925
• 10b Tejedor D, Cotos L, García-Tellado F. Org. Lett. 2011; 13: 4422
• 10c Cao H, Jiang H, Yao W, Liu X. Org. Lett. 2009; 11: 1931
• 10d Cao H, Jiang H, Mai R, Zhu S, Qi C. Adv. Synth. Catal. 2010; 352: 143
• 10e Cao H, Jiang H, Yuan G, Chen Z, Qi C, Huang H. Chem. Eur. J. 2010; 16: 10553
• 10f Jiang H, Yao W, Cao H, Huang H, Cao D. J. Org. Chem. 2010; 75: 5347

For selected recent examples, see:
• 11a Clark JS, Boyer A, Aimon A, Gurcía PE, Lindsay DM, Symington AD. F, Danoy Y. Angew. Chem. Int. Ed. 2012; 51: 12128
• 11b González J, González J, Pérez-Calleja C, López LA, Vicente R. Angew. Chem. Int. Ed. 2013; 52: 5853
• 11c Vicente R, González J, Riesgo L, González J, Lopez LA. Angew. Chem. Int. Ed. 2012; 51: 8063
• 11d Cao H, Zhan H, Cen J, Lin J, Lin Y, Zhu Q, Fu M, Jiang H. Org. Lett. 2013; 15: 1080
• 12a Jiang H, Zeng W, Li Y, Wu W, Huang L, Fu W. J. Org. Chem. 2012; 77: 5179
• 12b Num P, Dupuy S, Gaillard S, Poater A, Cavallo L, Nolan SP. Catal. Sci. Technol. 2011; 1: 58
• 12c Zheng Q, Hua R, Yin T. Curr. Org. Synth. 2013; 10: 161
• 12d Wang Y.-H, Liu H, Zhu L.-L, Li X.-X, Chen Z. Adv. Synth. Catal. 2011; 353: 707
• 12e Kramer S, Madsen JL. H, Rottländer M, Skrydstrup T. Org. Lett. 2010; 12: 2758

For selected recent examples, see:
• 13a Cui X, Xu X, Wojtas L, Kim MM, Zhang XP. J. Am. Chem. Soc. 2012; 134: 19981
• 13b He C, Guo S, Ke J, Hao J, Xu H, Chen H, Lei A. J. Am. Chem. Soc. 2012; 134: 5766
• 13c Yeh M.-CP, Lin M.-N, Hsu C.-H, Liang C.-J. J. Org. Chem. 2013; 78: 12381
• 13d Okamoto N, Yanada R. J. Org. Chem. 2012; 77: 3944
• 13e Yang Y, Yao J, Zhang Y. Org. Lett. 2013; 15: 3206
• 13f Li J, Liu L, Ding D, Sun J, Ji Y, Dong J. Org. Lett. 2013; 15: 2884
• 13g Butkevich AN, Meerpoel L, Stansfield I, Angibaud P, Corbu A, Cossy J. Org. Lett. 2013; 15: 3840
• 13h Jiang H, Cheng Y, Zhang Y, Yu S. Org. Lett. 2013; 15: 4884
• 13i Zheng M, Huang L, Wu W, Jiang H. Org. Lett. 2013; 15: 1838
• 13j Zheng X, Lu S, Li Z. Org. Lett. 2013; 15: 5432
• 13k Kramer S, Skrydstrup T. Angew. Chem. Int. Ed. 2012; 51: 4681
• 13l Huang X, Peng B, Luparia M, Gomes LF. R, Veiros LF, Maulide N. Angew. Chem. Int. Ed. 2012; 51: 8886
• 14 Schmidt B, Geißler D. Eur. J. Org. Chem. 2011; 4814 ; and references cited therein

For selected recent examples, see:
• 15a Zhang M, Jiang H.-F, Neumann H, Beller M, Dixneuf PH. Angew. Chem. Int. Ed. 2009; 48: 1681
• 15b Dheur J, Sauthier M, Castanet Y, Mortreux A. Adv. Synth. Catal. 2010; 352: 557
• 15c Chang S, Desai S, Leznoff DB, Merbouh N, Britton R. Eur. J. Org. Chem. 2013; 3219
• 15d Pridmore SJ, Slatford PA, Williams JM. J. Tetrahedron Lett. 2007; 48: 5111
• 15e Kel’in AV, Gevorgyan V. J. Org. Chem. 2002; 67: 95
• 15f Donohoe TJ, Fishlock LP, Lacy AR, Procopiou PA. Org. Lett. 2007; 9: 953
• 16a Chen Z, Li J, Jiang H, Zhu S, Li Y, Qi C. Org. Lett. 2010; 12: 3262
• 16b Chen Z, Huang G, Jiang H, Huang H, Pan X. J. Org. Chem. 2011; 76: 1134
• 17 Fukuda Y, Shiragami H, Utimoto K, Nozaki H. J. Org. Chem. 1991; 56: 5816
• 18 Preparation of 2,5-Disubstituted Furans from Enyne Acetates; Typical Procedure: To a mixture of (Z)-1,4-diphenylbut-1-en-3-yn-1-yl acetate (1a; 0.25 mmol) and MeNO₂ (1.0 mL), Pd(OAc)₂ (5 mol%), BF₃·OEt₂ (30 mol%), and H₂O (1 equiv) were added. The mixture was stirred at 80 °C for 10 h, then H₂O (10 mL) was added and the solution was extracted with EtOAc (3 × 8 mL). The combined extract was dried with anhydrous MgSO₄, the solvent was removed, and the residue was separated by column chromatography (petroleum ether–EtOAc, 30:1) to give the desired product 2a.