Isotope effects and the distinction between synchronous, asynchronous, and stepwise Diels-Alder reactions Academic Article

abstract

• A variety of symmetrical or nearly symmetrical Diels-Alder reactions are studied by a combination of experimental isotope effects, theoretical calculations, and rate observations. Becke3LYP calculations predicted highly asynchronous transition structures for Diels-Alder reactions of bis(boryl)acetylenes, dialkyl acetylenedicarboxylates, triazolinediones, and dialkyl maleates. Rate observations and kinetic isotope effects are consistent with these predictions, though the experimental support for the calculated structures is notably ambiguous in some cases. A concerted mechanism is supported for the retro-Diels-Alder reaction of norbornene. Overall, Diels-Alder reactions appear to be only very weakly biased toward synchronous transition states. 2001 Elsevier Science Ltd.

authors

• Singleton, Daniel

published proceedings

• TETRAHEDRON

altmetric score

• 7.992

author list (cited authors)

• Singleton, D. A., Schulmeier, B. E., Hang, C., Thomas, A. A., Leung, S. W., & Merrigan, S. R.

citation count

• 80

complete list of authors

• Singleton, DA||Schulmeier, BE||Hang, C||Thomas, AA||Leung, SW||Merrigan, SR

publication date

• June 2001

publisher

• Elsevier  Publisher

published in

• Tetrahedron: the international journal for the rapid publication of full original research papers and critical reviews in organic chemistr  Journal

keywords

• Asynchronous Transition State
• Diels-alder Reaction
• Isotope Effect

Digital Object Identifier (DOI)

• 10.1016/S0040-4020(01)00354-4

start page

• 5149

end page

• 5160

volume

• 57

issue

• 24

URL

• http%3A%2F%2Fdx.doi.org%2F10.1016%2Fs0040-4020%2801%2900354-4