Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”

Wang, Junpeng; Ong, Mitchell T.; Kouznetsova, Tatiana B.; Lenhardt, Jeremy M.; Martínez, Todd J.; Craig, Stephen L.

doi:10.1021/acs.joc.5b01493

Title: Catch and Release: Orbital Symmetry Guided Reaction Dynamics from a Freed “Tension Trapped Transition State”

Journal Article · Mon Aug 31 00:00:00 EDT 2015 · Journal of Organic Chemistry

DOI:https://doi.org/10.1021/acs.joc.5b01493· OSTI ID:1255180

Wang, Junpeng ^[1]; Ong, Mitchell T. ^[2]; Kouznetsova, Tatiana B. ^[1]; Lenhardt, Jeremy M. ^[2]; Martínez, Todd J. ^[3]; Craig, Stephen L. ^[1]

Duke Univ., Durham, NC (United States). Dept. of Chemistry
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
Stanford Univ., CA (United States). Dept. of Chemistry

The dynamics of reactions at or in the immediate vicinity of transition states are critical to reaction rates and product distributions, but direct experimental probes of those dynamics are rare. In this paper, s-trans, s-trans 1,3-diradicaloid transition states are trapped by tension along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the extensional forces generated by pulsed sonication of dilute polymer solutions. Once released, the branching ratio between symmetry-allowed disrotatory ring closing (of which the trapped diradicaloid structure is the transition state) and symmetry-forbidden conrotatory ring closing (whose transition state is nearby) can be inferred. Finally, net conrotatory ring closing occurred in 5.0 ± 0.5% of the released transition states, in excellent agreement with ab initio molecular dynamics simulations.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Stanford Univ., CA (United States); Duke Univ., Durham, NC (United States)

Sponsoring Organization:: USDOE; US Army Research Office (ARO)

Grant/Contract Number:: AC52-07NA27344; W911NF-07-0409

OSTI ID:: 1255180

Report Number(s):: LLNL-JRNL-663112

Journal Information:: Journal of Organic Chemistry, Vol. 80, Issue 23; ISSN 0022-3263

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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Steering chemical reactions with force Garcia-Manyes, Sergi; Beedle, Amy E. M. Nature Reviews Chemistry, Vol. 1, Issue 11 https://doi.org/10.1038/s41570-017-0083	journal	November 2017

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