Distortion, Tether, and Entropy Effects on Transannular Diels鈥揂lder Cycloaddition Reactions of 10鈥?8-Membered Rings

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• 作者：Cyndi Qixin He ; Tiffany Q. Chen ; Ashay Patel ; Sedef Karabiyikoglu ; Craig A. Merlic ; K. N. Houk
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：November 6, 2015
• 年：2015
• 卷：80
• 期：21
• 页码：11039-11047
• 全文大小：521K
• ISSN：1520-6904

文摘

Density functional theory calculations were performed on a set of 13 transannular Diels鈥揂lder (TADA) reactions with 10鈥?8-membered rings. The results were compared with those for bimolecular and intramolecular Diels鈥揂lder 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.