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10 but the details on its preparation are lacking. Reference 10b reports in a footnote that 2 can be prepared by reaction of the dianion of methyl acetoacetate with [(p-methoxybenzyl)-oxy]methyl chloride.
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0030029851
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We did not encounter significant problems with rearrangements in our preparation of 3. However, both a Brook rearrangement and a [1,2] TMS group shift have been reported for this same coupling under different conditions. See: (a) Cunico, R. F.; Nair, S. K. Synth. Commun. 1996, 26, 803.
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These conditions were first developed with ethyl acetoacetate as the β-keto ester component. The corresponding 2-alkenylfuran product was difficult to purify, however. Importantly, our originally reported conditions employing THF as a solvent were completely unsuccessful, resulting in no reaction. Use of ethanol at reflux led to product, but in low yields; reaction in dimethylformamide (starting at room temperature and warming to ca. 85 °C) was successful (55%) but not always reproducible. Reaction in acetonitrile at reflux was slow; but use of a hot 10:1 acetonitrile/water mixture resulted in reproducible yields of ca. 55%.
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0041496488
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(Z)-14 can be isomerized to the corresponding (E)-isomer, but this process is much slower than the isomerization of (Z)-6. Treatment of (Z)-14 with 10 equiv of diphenyl diselenide in tetrahydrofuran at reflux affords, after 8 d, a 4.4:1 (E):(Z) ratio of alkenes.
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48
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0002866211
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For methods for iododesilylation of vinylsilanes, see: (a) Chan, T. H.; Lau, P. W. K.; Mychajlowskij, W. Tetrahedron Lett. 1977, 18, 3317.
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0041997442
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1H NMR NOE spectroscopic studies on the vinyl iodide products. In the case of (Z)-6, a significant amount of alkene isomerization was noted, and the vinyl iodide product was isolated as a ca. 1:6 (E):(Z) mixture. In the case of (E)-7, little to no isomerization occurred.
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55
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0000217402
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Trost, B. M., Fleming, I., Paquette, L. A., Eds.; Pergamon: Oxford
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