Intramolecular Diels–Alder Reaction of a Biphenyl Group in a Strained meta-Quaterphenylene Acetylene

At elevated temperatures, a strained, cyclic meta-quaterphenylene acetylene undergoes an intramolecular cyclization reaction to form benz­[e]­indeno­[1,2,3-hi]­acephenanthrylene. This reaction represents an example of a Diels–Alder reaction at the 2-, 1-, 1′-, and 2′-positions of a biphenyl derivati...

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Bibliographic Details
Published in:Journal of organic chemistry 2024-07, Vol.89 (13), p.9620-9626
Main Authors: Mittal, Komal, Pham, Ashley V., Davis, Amanda G., Richardson, Abigail D., De Hoe, Clement, Dean, Ryan T., Baird, Vi, McDonald, Ashley Ringer, Frantz, Derik K.
Format: Article
Language:English
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Summary:At elevated temperatures, a strained, cyclic meta-quaterphenylene acetylene undergoes an intramolecular cyclization reaction to form benz­[e]­indeno­[1,2,3-hi]­acephenanthrylene. This reaction represents an example of a Diels–Alder reaction at the 2-, 1-, 1′-, and 2′-positions of a biphenyl derivative, a region analogous to the bay regions of perylene and other periacenes. The reaction proceeds cleanly with high conversion. Kinetics studies of a methylated derivative reveal that the ΔG ‡ for the reaction is ∼40–41 kcal/mol, and computational models predict a similar value of G rel for the transition state of a concerted [4 + 2]-cycloaddition.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.2c02280