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Updated: Feb 2, 2026

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry
Published on: August 25, 2016
Ambimodal Dipolar/Diels-Alder Cycloaddition Transition States Involving Proton Transfers
Shuming Chen1, Peiyuan Yu2, K N Houk1
1Department of Chemistry and Biochemistry , University of California , Los Angeles , California 90095-1569 , United States.
Abstract:
Quantum mechanical computations and molecular dynamics simulations have been used to elucidate the factors that control reaction outcomes in ambimodal transition states leading to both dipolar and Diels-Alder cycloaddition products, which can interconvert via α-ketol rearrangements. The dipolar cycloaddition pathways were found to be disadvantaged due to the persistence of charge separation after the second C-C formation en route to the dipolar cycloaddition adducts. Structural modifications that result in the stabilization of the charge-separated species lead to an increase in the amount of dipolar cycloadducts formed.
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