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Published May 8, 2024 | Published
Journal Article Open

Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions

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.

Copyright and License

© 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY-NC-ND 4.0.

Acknowledgement

The NIH-NIGMS (R35GM145239), Heritage Medical Research Investigators Program, and Caltech are thanked for the support of our research program. We further thank Professor Ken Houk for insightful discussions. The Caltech High Performance Computing Center is acknowledged for support of computational resources. P.-J.C. and C.S.S. would like to thank the NSF GRFP for funding. W.A.G. thanks the NSF (CBET-2311117) for support. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Contributions

P.-J.C and A.Q.C. contributed equally.

Data Availability

  • Complete computational details (PDF)

  • Cartesian coordinates of the calculated structures (ZIP)

  • Sample Progdyn Files (ZIP)

  • QM energies and analysis (XLSX)

  • Sample trajectory animations (ZIP)

Conflict of Interest

The authors declare no competing financial interest.

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Additional details

Created:
June 4, 2024
Modified:
June 4, 2024