W(CO)₅(L)-Catalyzed Cyclization of α-Alkynyl-β-dicarbonyl Derivatives: Synthesis of Methylenelactones, Furans, and Methylenecyclopentanes

Abstract

W(CO)₅(L)-Catalyzed cyclization of α-alkynyl-β-keto acids, keto esters, and diketones provides methylenelactones, furans, and methylenecyclopentanes via 5-exo-dig cyclization. Also, the present approach can be further applied to 5-endo-dig cyclization.

Key words

tungsten - cyclization - methylenelactones - furans - methylenecyclopentanes

• References and Notes

• 1a Dénès F, Pérez-Luna A, Chemla F. Chem. Rev. 2010; 110: 2366
• 1b Kirsch SF. Synthesis 2008; 3183
• 1c Alonso F, Beletskaya I, Yus M. Chem. Rev. 2004; 104: 3079
• 1d Zeni G, Larock RC. Chem. Rev. 2004; 104: 2285
• 1e Yamamoto Y, Radhakrishnan U. Chem. Soc. Rev. 1999; 28: 199
• 2a Belda O, Moberg C. Acc. Chem. Res. 2004; 37: 159
• 2b Li CL, Liu RS. Chem. Rev. 2000; 100: 3127
• 2c Bruneau C, Dixneuf PH. Acc. Chem. Res. 1999; 32: 311
• 2d Bruce MI. Chem. Rev. 1991; 91: 197
• 3a McDonald FE, Reddy KS. Angew. Chem. Int. Ed. 2001; 40: 3653
• 3b McDonald FE, Zhu HY. H. J. Am. Chem. Soc. 1998; 120: 4246
• 3c McDonald FE, Schultz CC. J. Am. Chem. Soc. 1994; 116: 9363
• 4a Koo B, McDonald FE. Org. Lett. 2005; 7: 3621
• 4b Davidson MH, McDonald FE. Org. Lett. 2004; 6: 1601
• 4c Bowman JL, McDonald FE. J. Org. Chem. 1998; 63: 3680
• 4d McDonald FE, Gleason MM. J. Am. Chem. Soc. 1996; 118: 6648
• 5a Onizawa Y, Kusama H, Iwasawa N. J. Am. Chem. Soc. 2008; 130: 802
• 5b Takaya J, Udagawa S, Kusama H, Iwasawa N. Angew. Chem. Int. Ed. 2008; 47: 4906
• 5c Kusama H, Yamabe H, Onizawa Y, Hoshino T, Iwasawa N. Angew. Chem. Int. Ed. 2005; 44: 468
• 5d Miura T, Kiyota K, Kusama H, Iwasawa N. Org. Lett. 2005; 7: 1445
• 5e Miura T, Iwasawa N. J. Am. Chem. Soc. 2002; 124: 518
• 5f Maeyama K, Iwasawa N. J. Am. Chem. Soc. 1998; 120: 1928
• 6a Ren W, Yamane M. J. Org. Chem. 2010; 75: 3017
• 6b Ren W, Yamane M. J. Org. Chem. 2009; 74: 8332
• 6c Sangu K, Fuchibe K, Akiyama T. Org. Lett. 2004; 6: 353
• 6d Wipf P, Graham TH. J. Org. Chem. 2003; 68: 8798
• 7 Kim S, Meng XJ. Org. Biomol. Chem. 2011; 9: 4429
• 8a Wakabayashi T, Ishii Y, Ishikawa K, Hidai M. Angew. Chem., Int. Ed. Engl. 1996; 35: 2123
• 8b Cavicchioli M, Bouyssi D, Gore J, Balme G. Tetrahedron Lett. 1996; 37: 1429
• 9a Elgafi S, Field LD, Messerle BA. J. Organomet. Chem. 2000; 607: 97
• 9b Chan DM. T, Marder TB, Milstein D, Taylor NJ. J. Am. Chem. Soc. 1987; 109: 6385
• 10a Corma A, Leyva-Perez A, Sabater MJ. Chem. Rev. 2011; 111: 1657
• 10b Genin E, Toullec PY, Antoniotti S, Brancour C, Genet JP, Michelet V. J. Am. Chem. Soc. 2006; 128: 3112
• 11a Míriam ÁC, Manuel MD, Ignacio RG. Chem. Rev. 2008; 108: 3174
• 11b Ogawa Y, Maruno M, Wakamatsu T. Synlett 1995; 871
• 12 Nakamura I, Yamamoto Y. Chem. Rev. 2004; 104: 2127
• 13a Lin J, Liu S, Sun B, Niu S, Li E, Liu X, Che Y. J. Nat. Prod. 2010; 73: 905
• 13b Montagon T, Tofi M, Vassilikogiannakis G. Acc. Chem. Res. 2008; 41: 1001
• 13c Lipshutz BH. Chem. Rev. 1986; 86: 795
• 14a D’Souza DM, Müller TJ. J. Chem. Soc. Rev. 2007; 36: 1095
• 14b Kirsch SF. Org. Biomol. Chem. 2006; 4: 2076
• 14c Brown RC. D. Angew. Chem. Int. Ed. 2005; 44: 850
• 14d Alonso F, Beletskaya IP, Yus M. Chem. Rev. 2004; 104: 3079
• 14e Nakamura I, Yamamoto Y. Chem. Rev. 2004; 104: 2127
• 14f Hou XL, Cheung HY, Hon TY, Kwan PL, Lo TH, Tong SY, Wong HN. C. Tetrahedron 1998; 54: 1955
• 15a Tsuji H, Yamagata KI, Ueda Y, Nakamura E. Synlett 2011; 1015
• 15b Feng X, Tan Z, Chen D, Shen Y, Guo CC, Xiang J, Zhu C. Tetrahedron Lett. 2008; 49: 4110
• 15c Ji WH, Pan YM, Zhao SY, Zhan ZP. Synlett 2008; 3046
• 15d Miki K, Yokoi T, Nishino F, Kato Y, Washitake Y, Ohe K, Uemura S. J. Org. Chem. 2004; 69: 1557
• 15e Kato Y, Miki K, Nishino F, Ohe K, Uemura S. Org. Lett. 2003; 5: 2619
• 16a Gao HY, Wu XX, Zhang JL. Chem.–Eur. J. 2011; 17: 2838
• 16b Aponick A, Li CY, Malinge J, Marques EF. Org. Lett. 2009; 11: 4624
• 16c Zhang JL, Schmalz HG. Angew. Chem. Int. Ed. 2006; 45: 6704
• 16d Yao T, Zhang X, Larock RC. J. Am. Chem. Soc. 2004; 126: 11164
• 17a Kusama H, Funami H, Shido M, Hara Y, Takaya J, Iwasawa N. J. Am. Chem. Soc. 2005; 127: 2709
• 17b Ohe K, Yokoi T, Miki K, Nishino F, Uemura S. J. Am. Chem. Soc. 2002; 124: 526
• 17c Iwasawa N, Shido M, Maeyama K, Kusama H. J. Am. Chem. Soc. 2000; 122: 10226
• 17d Ohe K, Miki K, Yokoi T, Nishino F, Uemura S. Organometallics 2000; 19: 5525
• 18a Alcázar E, Pletcher JM, McDonald FE. Org. Lett. 2004; 6: 3877
• 18b Sheng Y, Musaev DG, Reddy KS, McDonald FE, Morokuma K. J. Am. Chem. Soc. 2002; 124: 4149
• 19 Tiecco M, Testaferri L, Tingoli M, Marini F. J. Org. Chem. 1993; 58: 1349
• 20a Bouyssi D, Monteiro N, Balme G. Tetrahedron Lett. 1999; 40: 1297
• 20b Kitagawa O, Suzuki T, Inoue T, Watanabe Y, Taguchi T. J. Org. Chem. 1998; 63: 9470
• 20c Kitagawa O, Suzuki T, Inoue T, Taguchi T. Tetrahedron Lett. 1998; 39: 7357
• 21 McDonald FE, Olson TC. Tetrahedron Lett. 1997; 38: 7691
• 22 DABCO was also effective for the cyclization of keto ester 8a. Treatment of 8a with W(CO)₆ (0.2 equiv) and DABCO (1 equiv) in toluene at 350 nm at 40 °C for 18 h gave a mixture of 9a (80%) and 10a (14%)
• 23 Typical Procedure for the W(CO)₆-Catalyzed Cyclization of Acetylenic Acid 3d To a THF solution (2 mL) of acetylenic acid 3d (31 mg, 0.2 mmol) was added Et₃N (22 mg, 0.2 mmol) and W(CO)₆ (14 mg, 0.04 mmol) under nitrogen atmosphere at r.t. The mixture was irradiated at 350 nm under a photoreactor for 12 h. After the completion of the reaction, the mixture was quenched with H₂O and extracted with Et₂O (3 × 10 mL). The organic layer was washed with brine, dried with anhyd MgSO₄, and evaporated under reduced pressure. The crude product was purified by flash column chromatography (hexane–EtOAc = 30: 1) to give 4d (28 mg, 93%). ¹H NMR (400 MHz, CDCl₃): δ = 4.83 (dd, J = 4.6, 2.3 Hz, 1 H), 4.42 (dt, J = 2.8, 1.9 Hz, 1 H), 3.83 (s, 3 H), 3.76 (dd, J = 10.4, 7.6 Hz, 1 H), 3.32 (dd, J = 16.6, 7.6 Hz, 1 H), 3.15–3.03 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 169.5, 167.3, 153.1, 89.9, 53.4, 46.2, 29.4. ESI-HRMS: m/z calcd for C₇H₉O₄ [M + H]⁺: 157.0501; found: 157.0501. Typical Procedure for the W(CO)₆-Catalyzed Cyclization of α-Alkynyl-β-dicarbonyl Ester 13b To a toluene solution (2 mL) of α-alkynyl-β-dicarbonyl ester 13b (42 mg, 0.2 mmol) was added DABCO (22 mg, 0.2 mmol) and W(CO)₆ (14 mg, 0.04 mmol) under a nitrogen atmosphere at r.t., and then the mixture was irradiated at 350 nm. After the completion of the reaction, the mixture was quenched with H₂O (2 mL) and extracted with Et₂O (3 × 10 mL). The organic layer was washed with brine, dried with anhyd MgSO₄, and evaporated under reduced pressure. The crude product was purified by flash column chromatography (hexane–EtOAc = 20:1) to give the corresponding product 14b (34 mg, 82%). ¹H NMR (400 MHz, CDCl₃): δ = 6.01 (d, J = 5.6 Hz, 1 H), 5.94–5.77 (m, 1 H), 4.19 (qd, J = 7.1, 0.9 Hz, 2 H), 2.47–2.37 (m, 6 H), 1.61 (dd, J = 14.6, 7.3 Hz, 2 H), 1.26 (t, J = 7.1 Hz, 3 H), 0.89 (t, J = 7.4 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 206.0, 172.0, 136.1, 128.8, 73.4, 61.4, 40.7, 31.9, 30.1, 17.1, 14.1, 13.6. ESI-HRMS: m/z calcd for C₁₂H1₉O₃ [M + H]⁺: 211.1334; found: 211.1336