Copper(I)-Catalyzed Synthesis of Polysubstituted Furans from Alkynoates and 1,3-Dicarbonyl Compounds in the Presence of Oxygen

Abstract

A novel and straightforward synthesis of polysubstituted furans was achieved easily from the oxidative cyclization of 1,3-dicarbonyl compound and alkynoate catalyzed by CuI in the presence of O_2.

Key words

polysubstituted furans - oxidant - copper catalysis - oxygen.

References and Notes

• For selected reviews, see:
• 1a Lipshutz BH. Chem. Rev.  1986,  86:  795 
• 1b Dean FM. In Advances in Heterocyclic Chemistry   Vol. 31:  Katritzky AR. Academic Press; New York: 1983.  p.237 
• 1c Jeevanandam A. Ghule A. Ling YC. Curr. Org. Chem.  2002,  6:  841 
• 1d Brown RCD. Angew. Chem. Int. Ed.  2005,  44:  850 
• 1e Kirsh SF. Org. Biomol. Chem.  2006,  4:  2076 
• 1f Frère P. Skabara P. Chem. Soc. Rev.  2005,  34:  69 
• 2a Wong HNC. Yu P. Yick CY. Pure Appl. Chem.  1999,  71:  1041 
• 2b Lee K. Chan KF. Hui CW. Yim HK. Wu XW. Wong HNC. Pure Appl. Chem.  2005,  77:  139 
• 2c Kao CL. Chern JW. J. Org. Chem.  2002,  67:  6772 
• 2d Yang Z. Liu HB. Lee CM. Chang HM. Wong HNC. J. Org. Chem.  1992,  57:  7248 
• 2e Flynn BL. Hamel E. Jung MK. J. Med. Chem.  2002,  45:  2670 
• 2f Kerr DJ. Hamel E. Jung MK. Flynn BL. Bioorg. Med. Chem.  2007,  15:  3290 
• 2g Flynn BL. Pinard P. Hamel E. Org. Lett.  2001,  3:  651 
• 2h Wong HNC. Yang Y. Tetrahedron  1994,  50:  9583 
• 2i Gabriele B. Salerno G. Lauria E. J. Org. Chem.  1999,  64:  7687 
• 3 Minetto G. Raveglia LF. Sega A. Taddei M. Eur. J. Org. Chem.  2005,  24:  5277 ; and references cited therein
• 4a Hou XL. Cheung HY. Hon TY. Kwan PL. Lo TH. Tong SY. Wong HNC. Tetrahedron  1998,  54:  1955 
• 4b Krasnoslobodskaya LD. Gol’dfarb YL. Russ. Chem. Rev.  1969,  38:  389 
• 5a Hashmi ASK. Schwarz L. Choi JH. Frost TM. Angew. Chem. Int. Ed.  2000,  39:  2385 
• 5b Zhou CY. Chan PWH. Che CM. Org. Lett.  2006,  8:  325 
• 5c Liu WB. Jiang HF. Zhou P. Zhu SF. Synlett  2009,  3295 
• 5d Zhang M. Jiang HF. Wang AZ. Synlett  2007,  3241 
• 5e Cao H. Jiang HF. Yao WJ. Org. Lett.  2009,  11:  1931 
• 5f Yao T. Zhang X. Larock RC. J. Org. Chem.  2005,  70:  7679 
• 5g Patil NT. Wu H. Yamamoto Y. J. Org. Chem.  2005,  70:  4531 
• 5h Liu Y. Zhou S. Org. Lett.  2005,  7:  4609 
• 5i Sromek AW. Rubina M. Gevorgyan V. J. Am. Chem. Soc.  2005,  127:  10500 
• 5j Ma MS. Zhang J. Lu L. Chem. Eur. J.  2003,  9:  2447 
• 5k Suhre MH. Reif M. Kirsch SF. Org. Lett.  2005,  7:  3925 
• 5l Cadierno V. Crochet P. Curr. Org. Synth.  2008,  5:  343 
• 6 Li C.-J. Acc. Chem. Res.  2009,  42:  2335 ; and references therein
• For some reviews, see:
• 7a Punniyamurthy T. Velusamy S. Iqbal J. Chem. Rev.  2005,  105:  2329 
• 7b Stahl SS. Angew. Chem. Int. Ed.  2004,  43:  400 
• 8a Fan M. Guo L. Liu X. Liu W. Liang YM. Synthesis  2005,  391 
• 8b Fan M. Yan Z. Liu W. Liang YM. J. Org. Chem.  2005,  70:  8204 
• 8c Duan X. Liu X. Guo L. Liao M. Liu W. Liang YM. J. Org. Chem.  2005,  70:  6980 
• 8d Shu X.-Z. Liu X.-Y. Xiao H.-Q. Ji K.-G. Guo L.-N. Qi C.-Z. Liang Y.-M. Adv. Synth. Catal.  2008,  50:  243 
• 8e Shu X.-Z. Liu X.-Y. Ji K.-G. Xiao H.-Q. Liang Y.-M. Chem. Eur. J.  2008,  14:  5282 
• 8f Ji K.-G. Shen Y.-W. Shu X.-Z. Xiao H.-Q. Bian Y.-J. Liang Y.-M. Adv. Synth. Catal.  2008,  350:  1275 
• 8g Zhao L.-B. Guan Z.-H. Han Y. Xie Y.-X. He S. Liang Y.-M. J. Org. Chem.  2007,  72:  10276 
• 9 Christoffer J. Eur. J. Org. Chem.  1998,  7:  1259 
• 10a Sawada D. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2000,  122:  10521 
• 10b Gurjar MK. Maheshwar K. J. Org. Chem.  2001,  66:  7552 
• 10c Ying BP. Trogden BG. Kohlman DT. Liang SX. Xu YC. Org. Lett.  2004,  6:  1523 

11

General Procedure for the Preparation of Dimethyl But-2-yndioate and 1,3-Diphenyl-1,3-propanedione (3aa)
An oven-dried Schlenk tube was charged with CuI (9.5 mg, 0.05 mmol), 1a (0.50 mmol), and 2a (0.50 mmol). The Schlenk tube was sealed and then evacuated and backfilled with oxygen (3 cycles). Then DMF (2 mL) was added to the reaction system. The reaction was stirred at 110 ˚C under O₂ (1 atm) for 4 h. After cooling to r.t., the solvent diluted with Et₂O (10 mL) and washed with brine (5 mL) and dried over anhyd Na₂SO₄. After the solvent was evaporated in vacuo, the residues were purified by column chromatography, eluting with PE-EtOAc (10:1) to afford pure 3aa.
Dimethyl 4-Benzoyl-5-phenylfuran-2, 3-dicarboxylate (3aa) Yellow viscous oil. ^¹H NMR (400 MHz CDCl₃): δ = 3.61 (s, 3 H), 3.96 (s, 3 H), 7.29-7.39 (m, 5 H), 7.50-7.54 (m, 1 H), 7.61-7.63 (m, 2 H), 7.79-7.81 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 52.4, 52.5, 121.5, 126.2, 127.4, 127.6, 128.5, 128.6, 129.3, 130.2, 133.6, 136.7, 141.1, 155.3, 157.7, 161.9, 190.0. IR (neat): 694, 772, 899, 1080, 1167, 1235, 1443, 1666, 1730, 2953, 3004, 3062 cm^-¹. HRMS (EI): m/z calcd for C₂₁H₁₆O₆ [M + H]⁺: 365.1020; found: 365.1029.
The ^¹H NMR, ^¹³C NMR, IR, and HRMS data of 3aa-bb can be found in the Supporting Information.