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Calculations for 1 (X = NMs; Spartan '02, DFT-B3LYP; Møller Plesset MP2/6-31G** for frontier orbital energy calculations) indicate that formation of a copper acetylide significantly lowers the lowest unoccupied molecular orbital (LUMO), but also raises the energy of the highest occupied molecular orbital (HOMO) to some extent. Therefore, [4+2] cycloadditions with normal as well as inverse electron demand should both benefit from formation of an acetylide.
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Calculations for 1 (X = NMs; Spartan '02, DFT-B3LYP; Møller Plesset MP2/6-31G** for frontier orbital energy calculations) indicate that formation of a copper acetylide significantly lowers the lowest unoccupied molecular orbital (LUMO), but also raises the energy of the highest occupied molecular orbital (HOMO) to some extent. Therefore, [4+2] cycloadditions with "normal" as well as "inverse" electron demand should both benefit from formation of an acetylide.
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5J coupling between the bridgehead protons.
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X-ray crystal structure analysis of 35: C18H 21NO2S, Mr, 315.42 g mol-1, colorless plate, 0.15 x 0.05 x 0.05 mm, triclinic, space group P1, a, 8.9680(8, b, 14.2768(12, c, 14.4565(10) Å, α, 111.586(4, β, 98.551(4, γ, 105.550(3)°, V, 1593.7(2) Å3, T, 100 K, Z, 4, ρcalcd, 1.315 g cm3, λ, 0.71073 Å, μ(MoKα, 0.210 mm-1, Gaussian absorption correction (Tmin, 0.96, Tmax, 0.99, Nonius KappaCCD diffractometer, 2.97 < θ < 27.50, 17 724 measured reflections, 7230 independent reflections, 4175 reflections with I > 2σI, structure solved by direct methods and refined by full-matrix least-squares against F2 to R1, 0.075 [I > 2σ
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-3. CCDC-652457 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
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