Structural Investigations into the retro-Diels-Alder Reaction. Experimental and Theoretical Studies.
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 (13)C-(13)C 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.
Birney
David
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Contribution from the School of Chemistry, University of Melbourne, Parkville, Vic 3010, Australia, and Texas Tech University, Lubbock, Texas 79409-1061.
Lim
Tang Kuan
TK
Koh
Joanne H P
JH
Pool
Brett R
BR
White
Jonathan M
JM