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Distortion, Tether, and Entropy Effects on Transannular Diels-Alder Cycloaddition Reactions of 10-18-Membered Rings.
He, Cyndi Qixin; Chen, Tiffany Q; Patel, Ashay; Karabiyikoglu, Sedef; Merlic, Craig A; Houk, K N.
Afiliação
  • He CQ; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
  • Chen TQ; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
  • Patel A; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
  • Karabiyikoglu S; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
  • Merlic CA; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
  • Houk KN; Department of Chemistry and Biochemistry and ‡Department of Chemical and Biochemical Engineering, University of California , Los Angeles, California 90095, United States.
J Org Chem ; 80(21): 11039-47, 2015 Nov 06.
Article em En | MEDLINE | ID: mdl-26466172
Density functional theory calculations were performed on a set of 13 transannular Diels-Alder (TADA) reactions with 10-18-membered rings. The results were compared with those for bimolecular and intramolecular Diels-Alder reactions in order to investigate the controlling factors of the high TADA reactivities. The effects of tether length, heteroatoms, and alkynyl dienophiles on reactivity were analyzed. We found a correlation between tether length and reactivity, specifically with 12-membered macrocycles undergoing cycloaddition most readily. Furthermore, modifying 12-membered macrocycles by heteroatom substitution and utilizing alkynyl dienophiles enhances the reaction rates up to 10(5)-fold.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2015 Tipo de documento: Article
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2015 Tipo de documento: Article