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3, 50 MHz): δ = 19.5, 24.0, 26.8, 28.9, 32.0, 37.8, 48.7, 54.4, 77.2, 166.1.
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a values and the geometry of both reactants and products were fully optimized at B3LYP/6-31G* theory level: 1c, ΔE 14.08 kcal/mol; 1d, ΔE 13.51 kcal/mol; 1b, ΔE 5.09 kcal/mol; 1e, ΔE 4.59 kcal/mol; 1a, ΔE 0.0 kcal/mol; 1g, ΔE -3.98 kcal/mol; 1i, ΔE -5.46 kcal/mol; 1h, ΔE -5.76 kcal/mol; 1k, ΔE -5.51 kcal/mol; 1j, ΔE -5.71 kcal/mol. For leading references, see:
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1H NMR spectra of the ethyl derivatives 5b,d,f,k, where a multiplet or a double quartet collapsing at 50 °C into a quartet takes place for the ethyl quartet.
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51
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A concerted four-centers mechanism cannot be excluded, and investigation is currently underway. For a similar reaction recently reported in the literature, see: Mamaghani, M.; Badrian, A. Tetrahedron Lett. 2004, 45, 1547.
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