Structural investigations into the retro-Diels-alder reaction. Experimental and theoretical studies

David Birney, Tang Kuan Lim, Joanne H.P. Koh, Brett R. Pool, Jonathan M. White

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The manifestations of the retro-Diels Alder reaction in the ground-state structures of a range of cyclopentadiene and cyclohexadiene cycloadducts 9-15 have been investigated by a combination of techniques. These include low-temperature X-ray crystallography, density functional calculations (B3LYP/6-31G(d,p)) on both the ground states and transition states, and the measurement of 13C-13C coupling constants. We have found that the carbon - carbon bonds (labeled bonds a and b), which break in the rDA, are longer in the cycloadducts 9-15 than in their corresponding saturated analogues 9s-15s, which cannot undergo the rDA reaction. The degree of carbon - carbon bond lengthening appears to be related to the reactivity of the cycloadduct, thus the more reactive benzoquinone cycloadducts 5b and 13 have longer carbon - carbon bonds. Those cycloadducts 14 and 15 which are predicted to undergo asynchronous reactions show differing degrees of carbon - carbon bond lengthening, reflecting the differing degrees of bond breaking at the calculated transition states for the rDA.

Original languageEnglish
Pages (from-to)5091-5099
Number of pages9
JournalJournal of the American Chemical Society
Issue number18
StatePublished - May 8 2002


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