Flyby reaction trajectories: Chemical dynamics under extrinsic force

Yun Liu, Soren Holm, Jan Meisner, Yuan Jia, Qiong Wu, Toby J. Woods, Todd J. Martinez, Jeffrey S. Moore

Research output: Contribution to journalArticlepeer-review


Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. Here, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Computational modeling and simulations show that, besides altering energy barriers, the mechanical force activates reactive intramolecular motions nonstatistically, setting up “flyby trajectories” that advance directly to product without isomerization excursions. A mechanistic model incorporating nonstatistical dynamic effects accounts for isomer-dependent mechanochemical stereoselectivity.
Original languageEnglish (US)
Pages (from-to)208-212
Number of pages5
Issue number6551
StatePublished - Jul 9 2021

ASJC Scopus subject areas

  • General


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