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. with mixed aryl-alkyl, dialkyl, and terminal aromatic alkynes. However, numerous products were obtained in each case, which were not further investigated.
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34250822549
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The geometries computed at the various levels of theory were found to vary only insignificantly
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The geometries computed at the various levels of theory were found to vary only insignificantly.
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27
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34250903832
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-1 than the Z isomer:
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-1 than the Z isomer:
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29
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30
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34250793582
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Solvation effects, which were calculated using the PCM model as implemented in Gaussian03 did not result in significant changes of the barrier heights of any transition state 13 and 16, respectively.
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Solvation effects, which were calculated using the PCM model as implemented in Gaussian03 did not result in significant changes of the barrier heights of any transition state 13 and 16, respectively.
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This rearrangement has been calculated using methods involving high levels of electron correlation and basis sets; see for example: (a) A. P. Scott, R. H. Nobes, H. F. Schaefer, III, L. Radom, J. Am. Chem. Soc. 1994, 116, 10159. doi:10.1021/JA00101A039
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We did not investigate whether the reaction of NO3. with alkynes in the presence of excess NO3. leads to exclusive formation of 1,2-diketones, in order to support the assumed reversibility of the γ-fragmentation 12→17. Under such conditions, NO3. is trapped by NO2. to give N2O5, thus rendering this experiment insignificant
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5, thus rendering this experiment insignificant.
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37
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34250817729
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. are therefore highly unlikely.
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. are therefore highly unlikely.
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