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Intramolecular [2 + 2] photocycloaddition/thermal fragmentation: formally "allowed" and "forbidden"pathways toward
Scott J Bader1, Marc L Snapper
1Department of Chemistry, Merkert Chemistry Center, Boston College, 2609 Beacon Street, Chestnut Hill, Massachusetts 02467, USA.
Abstract:
The thermal fragmentation of highly functionalized, linear polycyclobutanes with a cis,syn,cis-relative stereochemistry is shown to offer a rapid entry into the dicyclopenta[a,d]cyclooctenyl (5-8-5) ring system. The thermolysis of polyfused cyclobutanes with a cis,syn,cis- or a cis,anti,cis-relationship proceeds in a formally "symmetry-allowed" manner through the intermediacy of a cis,trans-cyclooctadiene. When a bridging tether used to establish the cis,syn,cis-stereochemistry in the intramolecular [2 + 2] photocyclization is present in the thermolysis step, however, the result of a formally "symmetry-forbidden" fragmentation is observed yielding cis,cis-cyclooctadiene-containing 5-8-5 products. In general, the stereochemical observations noted in these fragmentations offer new opportunities for accessing a variety of stereochemical relationships in these 5-8-5 ring systems.
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