Pd-Catalyzed Diastereo- and Enantioselective [3+2]-Cycloaddition Reaction of Vinyl Epoxide with Nitroalkenes

Abstract

A diastereoselective and enantioselective [3+2]-cycloaddition reaction of vinyl epoxide and nitroalkenes has been developed using Pd/1,1′-ferrocene-P,N-ligand, providing substituted tetrahydrofurans in high yields and with high diastereo- and enantio­selectivities.

Key words

vinyl epoxide - nitroalkene - palladium - asymmetric catalysis - [3+2] cycloaddition

• References and Notes

• 1a Shim JG, Yamamoto Y. J. Org. Chem. 1998; 63: 3067
• 1b For related reactions on hydroxy allylic carbonates, see: Sekido M, Aoyagi K, Nakamura H, Kabuto C, Yamamoto Y. J. Org. Chem. 2001; 66: 7142
• 2a Aoyagi K, Nakamura H, Yamamoto Y. J. Org. Chem. 2002; 67: 5977
• 2b Patil NT, Yamamoto Y. Synlett 2007; 1994
• 2c Patil NT, Yamamoto Y. Top. Organomet. Chem. 2006; 19: 91
• 2d Lowe MA, Ostovar M, Ferrini S, Chen CC, Lawrence PG, Fontana F, Calabrese AA, Aggarwal VK. Angew. Chem. Int. Ed. 2011; 50: 6370
• 2e Fontana F, Chen CC, Aggarwal VK. Org. Lett. 2011; 13: 3454
• 3a Morizawa Y, Oshima K, Nozaki H. Tetrahedron Lett. 1982; 23: 2871
• 3b Shimizu I, Ohashi Y, Tsuji J. Tetrahedron Lett. 1985; 26: 3825
• 3c Hiroi K, Yamada A. Tetrahedron: Asymmetry 2000; 11: 1835
• 3d Trost BM, Morris PJ. Angew. Chem. Int. Ed. 2011; 50: 6167
• 4a Shimizu I, Ohashi Y, Tsuji J. Chem. Lett. 1987; 6: 1157
• 4b Trost BM, Fandrick DR. J. Am. Chem. Soc. 2003; 125: 11836
• 5 Larksarp C, Alper H. J. Org. Chem. 1998; 63: 6229
• 6a Parsons AT, Campbell MJ, Johnson JS. Org. Lett. 2008; 10: 2541
• 6b For chiral Lewis acid catalyzed [3+2] cycloaddition of cyclopropanes with aldehydes and imines, see: Parsons AT, Johnson JS. J. Am. Chem. Soc. 2009; 131: 3122
• 6c See also: Parsons AT, Smith AG, Neel AJ, Johnson JS. J. Am. Chem. Soc. 2010; 132: 9688
• 7a Elliott MC. J. Chem. Soc., Perkin Trans. 1 1998; 4175
• 7b Elliott MC. J. Chem. Soc., Perkin Trans. 1 2002; 2301
• 7c Wolfe JP, Hay MB. Tetrahedron 2007; 63: 261
• 8a Faul MM, Huff BE. Chem. Rev. 2000; 100: 2407
• 8b Bermejo A, Figadere B, Zafra-Polo MC, Barrachina I, Estornell E, Cortés D. Nat. Prod. Rep. 2005; 22: 269
• 8c Saleem M, Kim HJ, Ali MS, Lee YS. Nat. Prod. Rep. 2005; 22: 696
• 8d Kang EJ, Lee E. Chem. Rev. 2005; 105: 4348
• 9a Wu H, Wu XW, Hou XL, Dai LX. Chin. J. Chem. 2002; 20: 816
• 9b Hou XL, Dong DX, Yuan K. Tetrahedron: Asymmetry 2004; 15: 2189
• 9c Wu W.-Q, Peng Q, Dong D.-X, Hou X.-L, Wu Y.-D. J. Am. Chem. Soc. 2008; 130: 9717
• 9d Ding C.-H, Hou X.-L. Bull. Chem. Soc. Jpn. 2010; 83: 992
• 10 Zhang W, Yoneda Y, Kida T, Nakatsuji Y, Ikeda I. Tetrahedron: Asymmetry 1998; 9: 3371
• 11a Ahn KH, Cho CW, Baek HH, Park J, Lee S. J. Org. Chem. 1996; 61: 4937
• 11b Deng W.-P, You S.-L, Hou X.-L, Dai L.-X, Yu Y.-H, Xia W, Sun J. J. Am. Chem. Soc. 2001; 123: 6508
• 11c Tu T, Deng W.-P, Hou X.-L, Dai L.-X, Dong X.-C. Chem. Eur. J. 2003; 9: 3073
• 12 Typical Procedure for the Cycloaddition Reaction of Vinyl Epoxide 1a with Nitroalkenes 2: A Schlenk tube with a magnetic stir bar was charged with Pd₂dba₃⋅CHCl₃ (6.2 mg, 0.006 mmol), ligand L5h (6.6 mg, 0.012 mmol), and THF (1.5 mL) under an argon atmosphere. The resulting solution was allowed to stir for 30 min before nitroalkene 2a (30 mg, 0.20 mmol) followed by vinyl epoxide 1a (40 μL, 0.40 mmol) were added. The reaction mixture was allowed to stir for about 24 h at r.t. (26 °C) until the reaction was complete (monitored by TLC). The reaction mixture was diluted with CH₂Cl₂ (2 mL) before being passed through a short plug of silica gel to remove the palladium black. After the filtrate was concentrated, the crude product was analyzed by ¹H NMR spectroscopy to determine the diastereomeric ratio, and then the residue was purified by flash chroma-tography on silica gel (eluent: EtOAc–PE) to afford 32 mg of the product 3a as a light yellow liquid. Analytical Data for 3a: ¹H NMR (300 MHz, CDCl₃): δ = 1.39 (s, 3 H), 3.95 (d, J = 8.7 Hz, 1 H), 4.23 (d, J = 8.7 Hz, 1 H), 4.64 (d, J = 6.0 Hz, 1 H), 5.24–5.31 (m, 2 H), 5.62 (d, J = 6.0 Hz, 1 H), 5.88 (dd, J = 11.1, 17.7 Hz, 1 H), 7.33–7.39 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 23.43, 50.78, 77.64, 83.39, 100.65, 118.02, 125.31, 128.41, 128.84, 135.65, 138.82. IR (KBr): 2978, 2880, 1552, 1068 cm^–1. MS (EI): m/z (%) = 233 (8.88) [M⁺], 171 (100). HRMS (EI): m/z calcd for C₁₃H₁₅NO₃: 233.1052; found: 233.1042. HPLC (Chiralcel OJ-H 0.46 cm × 25 cm, n-hexane–i-PrOH (65:35); flow rate: 0.7 mL/min, UV: λ = 230 nm), t _R = 10.0 min (minor), 12.6 min (major)
• 13 The crystallographic data are deposited at the Cambridge Crystallographic Data Centre under deposition number CCDC 865918