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(a) The reaction of dimethyl methylmalonate with alkynes gave only a trace amount of the adducts even after a prolonged reaction time, although the reaction of methyl malononitrile gave the desired allylation product in high yields.5a
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26
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4644226476
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note
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1H NMR spectra, the methyne proton of methyl malononitrile appears at δ 3.77. On the other hand, the methyne proton of dimethyl methylmalonate and 1a (vide infra) appears at δ 3.44 and 2.30, respectively. This indicates that the methyne proton of methyl malononitrile is more acidic than dimethyl methylmalonate and 1a.
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27
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4644297615
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note
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We ran the reaction at higher concentration because we observed that at lower concentrations the reaction became slower.
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The addition of cyclic β-keto esters to Michael acceptor is known, see: (a) Ooi, T.; Miki, T.; Taniguchi, M.; Shiraishi, M.; Takeuchi, M.; Maruoka, K. Angew. Chem., Int. Ed. 2003, 42, 3796-3798 and references therein. The direct intramolecular addition of cyclic β-keto esters to alkynes and alkenes is known; see:
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