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

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 rea...

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Published in:Journal of organic chemistry 2015-11, Vol.80 (21), p.11039-11047
Main Authors: He, Cyndi Qixin, Chen, Tiffany Q, Patel, Ashay, Karabiyikoglu, Sedef, Merlic, Craig A, Houk, K. N
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cited_by cdi_FETCH-LOGICAL-a374t-b770c11b901003f2ae741ebe6afb701994e3297e2b7e6476730a2c1670eb723
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description 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.
doi_str_mv 10.1021/acs.joc.5b02288
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title Distortion, Tether, and Entropy Effects on Transannular Diels–Alder Cycloaddition Reactions of 10–18-Membered Rings
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