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Distortion, Tether, and Entropy Effects on Transannular Diels-Alder Cycloaddition Reactions of 10-18-Membered Rings

Authors :
Cyndi Qixin He
Sedef Karabiyikoglu
Kendall N. Houk
Craig A. Merlic
Tiffany Chen
Ashay Patel
Source :
He, CQ; Chen, TQ; Patel, A; Karabiyikoglu, S; Merlic, CA; & Houk, KN. (2015). Distortion, Tether, and Entropy Effects on Transannular Diels-Alder Cycloaddition Reactions of 10-18-Membered Rings. Journal of Organic Chemistry, 80(21), 11039-11047. doi: 10.1021/acs.joc.5b02288. UCLA: Retrieved from: http://www.escholarship.org/uc/item/9gx8b7p8, The Journal of organic chemistry, vol 80, iss 21
Publication Year :
2015
Publisher :
eScholarship, University of California, 2015.

Abstract

© 2015 American Chemical Society. 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 105-fold.

Details

Language :
English
Database :
OpenAIRE
Journal :
He, CQ; Chen, TQ; Patel, A; Karabiyikoglu, S; Merlic, CA; & Houk, KN. (2015). Distortion, Tether, and Entropy Effects on Transannular Diels-Alder Cycloaddition Reactions of 10-18-Membered Rings. Journal of Organic Chemistry, 80(21), 11039-11047. doi: 10.1021/acs.joc.5b02288. UCLA: Retrieved from: http://www.escholarship.org/uc/item/9gx8b7p8, The Journal of organic chemistry, vol 80, iss 21
Accession number :
edsair.doi.dedup.....fa028d47e9c1ee667696f1fbc01fe825
Full Text :
https://doi.org/10.1021/acs.joc.5b02288.