Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions

Peng Jui Chen; Alexander Q. Cusumano; Kaylin N. Flesch; Christian Santiago Strong; William A. Goddard; Brian M. Stoltz

doi:10.1021/jacs.4c02681

Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions

Peng Jui Chen
, Alexander Q. Cusumano
, Kaylin N. Flesch
, Christian Santiago Strong
, William A. Goddard
, Brian M. Stoltz

Division of Chemistry and Chemical Engineering
Beckman Institute

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	12758-12765
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	146
Issue number	18
DOIs	https://doi.org/10.1021/jacs.4c02681
Publication status	Published - 8 May 2024
Externally published	Yes

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10.1021/jacs.4c02681

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title = "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.",

author = "Chen, \{Peng Jui\} and Cusumano, \{Alexander Q.\} and Flesch, \{Kaylin N.\} and Strong, \{Christian Santiago\} and Goddard, \{William A.\} and Stoltz, \{Brian M.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society",

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doi = "10.1021/jacs.4c02681",

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AU - Chen, Peng Jui

AU - Cusumano, Alexander Q.

AU - Flesch, Kaylin N.

AU - Strong, Christian Santiago

AU - Goddard, William A.

AU - Stoltz, Brian M.

PY - 2024/5/8

Y1 - 2024/5/8

N2 - 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.

AB - 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.

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DO - 10.1021/jacs.4c02681

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AN - SCOPUS:85192079558

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SP - 12758

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

Molecular Dynamics Investigations of Dienolate [4 + 2] Reactions

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