Organocatalytic [3+2] Annulation of β-Tetralones with α,β-Unsaturated Aldehydes

Abstract

The NBS-mediated organocatalytic cascade synthesis of 4,5-dihydronaphtho[2,1-b]furan-1-carbaldehydes from α,β-unsaturated aldehydes and 2-tetralones have been developed. In this synthesis strategy, the C1 of in situ generated brominated 2-tetralone was used as identical twin electron donor–acceptor, and the Cβ and Cα of enals were used as the heterogeneous twin electron acceptor–donors. The process has been realized by a synergistic amine/p-TSA catalyzed one-pot cascade Michael addition–cyclopropanation–ring opening–oxa-Michael addition under mild conditions and without the use of transition metals.

Key words

organocatalysis - cascade reaction - [3+2] annulation - 2-tetralone - 4,5-dihydronaphtho[2,1-b]furan

• References and Notes

• 1 Volla CM. R, Atodiresei I, Rueping M. Chem. Rev. 2013; 114: 2390
• 2 Chauhan P, Mahajan S, Kaya U, Hack D, Enders D. Adv. Synth. Catal. 2015; 357: 253
• 3 Zhang X.-S, Song X, Li H, Zhang S.-L, Chen X.-B, Yu X.-H, Wang W. Angew. Chem. Int. Ed. 2012; 51: 7282
• 4 Zhou H, Zhang H, Mu S, Zhang W.-Z, Ren W.-M, Lu X.-B. Green Chem. 2019; 21: 6335
• 5 Huang J, Li F, Cui L, Su S, Jia X, Li J. Chem. Commun. 2020; 56: 4555
• 6 Kumar I, Ramaraju P, Mir NA. Org. Biomol. Chem. 2013; 11: 709
• 7 Zhang L, Fu N, Luo S. Acc. Chem. Res. 2015; 48: 986
• 8 Wang Y, Du D.-M. Org. Chem. Front. 2020; 7: 3266
• 9 Jia Z.-J, Jiang H, Li J.-L, Gschwend B, Li Q.-Z, Yin X, Grouleff J, Chen Y.-C, Jørgensen KA. J. Am. Chem. Soc. 2011; 133: 5053
• 10 Zeng X.-F, Ni Q.-J, Raabe G, Enders D. Angew. Chem. Int. Ed. 2013; 52: 2977
• 11 Akhtar MS, Thombal RS, Tamargo RJ. I, Yang W.-G, Kim S.-H, Lee YR. Green Chem. 2020; 22: 4523
• 12 List B, Lerner RA, Barbas CF. III. J. Am. Chem. Soc. 2000; 122: 2395
• 13 Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007; 107: 5471
• 14 Notz W, Tanaka F, Barbas CF. III. Acc. Chem. Res. 2004; 37: 580
• 15 Ahrendt KA, Borths CJ, MacMillan DW. C. J. Am. Chem. Soc. 2000; 122: 4243
• 16 Erkkilä A, Majander I, Pihko PM. Chem. Rev. 2007; 107: 5416
• 17 Murakami C, Lago JH. G, Perazzo FF, Ferreira KS, Lima ME. L, Moreno PR. H, Young MC. M. Chem. Biodiversity 2013; 10: 621
• 18 Li S, Yao Y, Tang Z, Sun B, Yu C, Li T, Yao C. Org. Biomol. Chem. 2019; 17: 268
• 19 Clavin ML, Gorzalczany C, Mino J, Kadarian C, Martino V, Ferraro G, Acevedo C. Phytother. Res. 2000; 14: 275
• 20 Clavin M, Lorenzen K, Mayer A, Martino V, Anke T. Acta Hortic. 1999; 501: 277
• 21 Chavan SP, Dhondge VD, Patil SS, Rao YT. S, Gvande CA. Tetrahedron: Asymmetry 1997; 8: 2517
• 22 Miller B, Shi X. J. Org. Chem. 1992; 57: 1677
• 23 Li Z, Zhang H, Zhao L, Ma Y, Wu Q, Ren H, Lin Z, Zheng J, Yu X. Chem. Commun. 2024; 60: 3579
• 24 General Procedures for [3+2] Annulation Reaction a (1.0 mmol, 1.0 equiv), NBS (1.1 mmol, 1.1 equiv) and p-TSA (0.1 mmol, 0.1 equiv) were added to 5 mL CHCl₃ sequentially and stirred at 25 °C. When a was transformed completely in almost 20 min, b (0.8 mmol, 0.8 equiv), NaOAc (2.0 mmol, 2.0 equiv), and Cat. I (0.2 mmol, 0.2 equiv) were added sequentially to the mixture and stirred at 60 °C. When the reaction was completed, the reaction mixture was filtered and concentrated under reduce pressure. The residue was purified by silica gel column chromatography using a 200:1 mixture of petrol ether/ethyl acetate.