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We tried other bases: Calcium carbonate was not as efficient as sodium acetate and proton scavengers tertiary amines, proton sponge, or 2, 3-dimethylbut-2-ene either inhibited the reaction completely, giving a strong blue color amines, and/or gave very small yields of the adduct
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We tried other bases: Calcium carbonate was not as efficient as sodium acetate and proton scavengers (tertiary amines, proton sponge, or 2, 3-dimethylbut-2-ene) either inhibited the reaction completely, giving a strong blue color (amines), and/or gave very small yields of the adduct.
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The extreme purity of the cycloadduct obtained with this reductant is remarkable. At the end of the four cycles an insoluble red precipitate was formed, whereas the supernatant was colorless and CO uptake was definitely stopped. Plausibly, the resulting tetraaminodicarbenium dihalide trapped the degraded NiII in an insoluble polymeric cationic complex, although this has not been further investigated
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The extreme purity of the cycloadduct obtained with this reductant is remarkable. At the end of the four cycles an insoluble red precipitate was formed, whereas the supernatant was colorless and CO uptake was definitely stopped. Plausibly, the resulting tetraaminodicarbenium dihalide trapped the degraded NiII in an insoluble polymeric cationic complex, although this has not been further investigated.
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The attempted esterification of the crude product with methanol at reflux and a catalytic amount of p-toluenesulfonic acid led again to 3a. All attempts to silylate, methylate, or acylate the hydroxy functionality also failed
-
The attempted esterification of the crude product with methanol at reflux and a catalytic amount of p-toluenesulfonic acid led again to 3a. All attempts to silylate, methylate, or acylate the hydroxy functionality also failed.
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Although almost all the spectral data and chemical behavior is indicative of this structure, one of the referees disagrees with us
-
Although almost all the spectral data and chemical behavior is indicative of this structure, one of the referees disagrees with us.
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48
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77955440727
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13C NMR experiment showed no significant differences in the spectrum
-
13C NMR experiment showed no significant differences in the spectrum.
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50
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77955435370
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an experiment performed under carbonylative conditions in the absence of the nickel salt gave only 1, 5-hexadiene; c
-
an experiment performed under carbonylative conditions in the absence of the nickel salt gave only 1, 5-hexadiene; c)
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Unlike externally added alcohols, an alkynol can coordinate the active metal center, its distal hydroxy functionality approaching the appropriate intermediate. Hence a high yield of the ester may arise
-
Unlike externally added alcohols, an alkynol can coordinate the active metal center, its distal hydroxy functionality approaching the appropriate intermediate. Hence a high yield of the ester may arise.
-
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59
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77955460928
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Plain unconjugated olefins like 1, 5-hexadiene do not undergo the carbonylative cycloaddition reaction with allyl halides. Electrophilic attack of an allylic iron halide by allyl halide would result in the release of uncoordinated 1, 5-hexadiene
-
Plain unconjugated olefins like 1, 5-hexadiene do not undergo the carbonylative cycloaddition reaction with allyl halides. Electrophilic attack of an allylic iron halide by allyl halide would result in the release of uncoordinated 1, 5-hexadiene.
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