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The reaction rate for the [(SIMes)CuBr]-catalyzed cycloaddition of 1a to 2a in DMSO showed a first-order dependence on the concentration of [(SIMes)CuBr] (6.5-50.4 mM, see Supporting Information). In the case of [(SIMes)CuBr], the cycloaddition of internal alkynes efficiently proceeded. On the other hand, no cycloaddition of internal alkynes proceeded in the presence of the precatalyst I. The discrepancy suggests that the [(SIMes)CuBr]-catalyzed cyclization likely proceeds in a different way in comparison with the I-mediated cycloaddition.
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The reaction rate for the [(SIMes)CuBr]-catalyzed cycloaddition of 1a to 2a in DMSO showed a first-order dependence on the concentration of [(SIMes)CuBr] (6.5-50.4 mM, see Supporting Information). In the case of [(SIMes)CuBr], the cycloaddition of internal alkynes efficiently proceeded. On the other hand, no cycloaddition of internal alkynes proceeded in the presence of the precatalyst I. The discrepancy suggests that the [(SIMes)CuBr]-catalyzed cyclization likely proceeds in a different way in comparison with the I-mediated cycloaddition.
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After the reaction was completed, the precipitate was recovered by addition of an excess amount of toluene (precipitation method) to the reaction solution. The copper content in the filtrate was less than 1% of that in fresh I, indicating that the copper species hardly leaches into the reaction solution. The elemental analysis and 1H NMR spectrum of the recovered precipitate showed that the recovered I consists of one molecule of dicopper-substituted silicotungstate and two molecules of 3a. The UV-vis spectrum of the recovered I agreed well with that of the sum of fresh I and 3a, suggesting that the γ-Keggin structure of the recovered I is retained after the cycloaddition. No absorption bands at 700 nm due to the d-d transition of the copper(II) species was observed in the UV-vis spectrum of the recovered I, suggesting the presence of the reduced copper(I) species in the recovered I
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1H NMR spectrum of the recovered precipitate showed that the recovered I consists of one molecule of dicopper-substituted silicotungstate and two molecules of 3a. The UV-vis spectrum of the recovered I agreed well with that of the sum of fresh I and 3a, suggesting that the γ-Keggin structure of the recovered I is retained after the cycloaddition. No absorption bands at 700 nm due to the d-d transition of the copper(II) species was observed in the UV-vis spectrum of the recovered I, suggesting the presence of the reduced copper(I) species in the recovered I.
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