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Elucidation of Selectivity Difference in the Diels-Alder Reactions of 6,6-Disubstituted Cyclohexa-2,4-dienone


초록

Recently it was reported that cycloaddition of 6,6-disubstituted cyclohexa-2,4-dienone, 1 with cyclopentadiene gave solely the adduct of type 1.while its reaction with 1,3-cyclohexadiene gave both Ⅱ and Ⅲ. Semiempirical MO calculations were done to elucidate the origin of the selectivity difference between the two dienes. Cycloaddition of 1 with cyclopentadiene is controlled thermodynamically to give only 1-diene adduct by ΔGvalues of 10.6-20.3 kcal/mol, while its reaction with 1,3-cyclohexadiene does not show 1-diene/1-dienophile selectivity due to similar stabilities of the two adducts. Thermodynamic parameters also show that 두애 adducts are more fabourably fromed in the cycloadditions of 1 with both cyclopentadiene and 1,3-cyclohexadiene, which coincides with experimental observations. Cope rearrangements of endo adducts are another avenue to convert between 1-diene and 1-dienophile.

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피인용 문헌

  1. ChemInform Abstract: Elucidation of Selectivity Difference in the Diels-Alder Reactions of 6,6-Disubstituted Cyclohexa-2,4-dienone vol.33, pp.43, 2010, https://doi.org/10.1002/chin.200243026
  2. -Quinol Dimers vol.76, pp.21, 2011, https://doi.org/10.1021/jo201658y
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  5. Regioselective Multicomponent Synthesis of 2,4,6‐Trisubstituted Phenols from Fischer Alkynyl Carbene Complexes vol.2016, pp.7, 2002, https://doi.org/10.1002/ejoc.201501211