Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions
Peng-Jui Chen, Alexander Q. Cusumano, Kaylin N. Flesch, Christian Santiago Strong, William A. Goddard III, Brian M. Stoltz
2024J. Am. Chem. Soc., 146(18), 12758-12765
Abstract
We report quantum mechanics calculations and quasiclassical trajectory simulations of [4 + 2] reactions using three common dienolate substrates: siloxy dienes, Li dienolates, and conjugated Pd enolates. Asynchronous transition structures and unequal bond formation were invariably found, with average time gaps of developing bonds ranging from 26.5 to >251.0 fs. The results display a spectrum of dynamically concerted and stepwise [4 + 2] reactions, offering insights into the origin of the stereochemical outcomes of such reactions.
Cite this publication
Chen, P., Cusumano, A. Q., Flesch, K. N., Strong, C. S., III, W. A. G., & Stoltz, B. M. (2024). Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions. *J. Am. Chem. Soc.*, *146*(18), 12758-12765. https://doi.org/10.1021/jacs.4c02681