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Synlett 2012; 23(7): 1035-1038
DOI: 10.1055/s-0031-1290525
DOI: 10.1055/s-0031-1290525
letter
Pd-Catalyzed Diastereo- and Enantioselective [3+2]-Cycloaddition Reaction of Vinyl Epoxide with Nitroalkenes
Weitere Informationen
Publikationsverlauf
Received: 12. Januar 2012
Accepted after revision: 12. Februar 2012
Publikationsdatum:
29. März 2012 (online)
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.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
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- 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