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Throwing a curve: The first example of a through‐bond stereoelectronic effect for curved aromatic compounds is described for buckybowls, that is, benzylic‐substituted sumanenes. Methyl‐ and hydroxysumanene favor the endo‐R conformer because of a difference in the strength, between the conformers, of the hyperconjugation of the benzylic CH bond with the bowl.
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