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...

Full description

Saved in:
Bibliographic Details
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
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.5b02288