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Abstract Dynamic motion often controls selectivity in reactions featuring two consecutive potential‐energy transition states. Here we report density functional theory (DFT)‐based direct dynamics trajectories and machine learning classification analysis for cyclopentadienone dimerization and a N 2 extrusion reaction leading to semibullvalene. These reactions have consecutive transition states, and there is dynamic selectivity that determines which of two possible C‐C bonds is formed after the first transition state. For cyclopentadienone dimerization with a bispericyclic first transition state, machine learning analysis using transition‐state based features provided >90% trajectory classification accuracy, but only using AdaBoost and random forest algorithms. Many other relatively sophisticated machine learning algorithms showed poor accuracy despite the obvious motion responsible for selectivity. Feature importance analysis confirmed that the sigmatropic rearrangement vibrational motion in the bispericyclic transition state provides prediction of which of the second C‐C bonds is dynamically formed. For the reaction leading to semibullvalene, machine learning analysis provides solid accuracy for classifying trajectories and predicting which C‐C bond is formed and which C‐C bond is broken immediately after N 2 ejection. Like the cyclopentadienone dimerization reaction, machine learning feature importance analysis showed that the sigmatropic rearrangement vibrational motion in the N 2 extrusion transition state determines which C‐C bond is formed and which is broken. Surprisingly, machine learning struggles to predict which trajectories undergo a subsequent [3,3] sigmatropic rearrangement process, which isomerizes equivalent forms of semibullvalene.
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Photomechanochemical control over stereoselectivity in the [2 + 2] photodimerization of acenaphthylene
Tuning solubility and mechanical activation alters the stereoselectivity of the [2 + 2] photochemical cycloaddition of acenaphthylene. Photomechanochemical conditions produce the syn cyclobutane, whereas the solid-state reaction in the absence of mechanical activation provides the anti . When the photochemical dimerization occurs in a solubilizing organic solvent, there is no selectivity. Dimerization in H 2 O, in which acenaphthylene is insoluble, provides the anti product. DFT calculations reveal that insoluble and solid-state reactions proceed via a covalently bonded excimer, which drives anti selectivity. Alternatively, the noncovalently bound syn conformer is more mechanosusceptible than the anti , meaning it experiences greater destabilization, thereby producing the syn product under photomechanochemical conditions. Cyclobutanes are important components of biologically active natural products and organic materials, and we demonstrate stereoselective methods for obtaining syn or anti cyclobutanes under mild conditions and without organic solvents. With this work, we validate photomechanochemistry as a viable new direction for the preparation of complex organic scaffolds.
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- Award ID(s):
- 2112550
- PAR ID:
- 10431067
- Date Published:
- Journal Name:
- Faraday Discussions
- Volume:
- 241
- ISSN:
- 1359-6640
- Page Range / eLocation ID:
- 266 to 277
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2FD00122E
