Transition-State Steric Fields Capture Geometric Signatures Associated with Electronic Perturbations in Asymmetric Catalysis
- 1RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, Japan, 351-0198
Abstract
In data analysis of molecular catalysis, molecular shape can be represented by voxel descriptors generated by mapping molecular structures onto a three-dimensional grid according to atomic van der Waals radii. Such voxel representations of molecular shape can be treated as steric molecular fields and are generally used as steric descriptors. However, because electronic perturbations can lead to systematic changes in molecular geometry, steric fields constructed from transition-state (TS) structures may also capture geometric signatures. We therefore examined whether steric fields derived from TS geometries can capture such structural changes associated with electronic perturbations in asymmetric catalysis. Using DFT-calculated TS structures from three asymmetric Michael addition systems, we generated two voxel-based molecular-field representations, steric fields and NPA-charge fields, for the major and minor TS pathways and used them to construct regression models with calculated enantioselectivity (ΔΔ G ‡ ) as the target variable. The resulting steric- and NPA-charge field models showed similar pathway-dependent trends in cross-validated coefficients of determination (q 2 ). The NPA-charge fields revealed distinct charge responses across the three reaction systems, and the associated changes in TS geometry were captured by the steric fields. These results indicate that TS-derived steric fields can encode not only molecular shape but also the geometric changes associated with electronic perturbations, providing simple and interpretable descriptors for data analysis in asymmetric catalysis.
Related
- Transient absorption signatures of asymmetric carrier cooling in semiconductors
- Structural and electronic signatures of stacking and intralayer transitions in epitaxial bilayer WSe2 on GaP(111)B
- Broadband asymmetric transmission and cross-polarization conversion in an interlayer-coupled bilayer chiral metasurface
- Asymmetric synthesis of azabicyclo[2.1.1]hexanes via electrochemical haloamination of methylenecyclobutanes
- Asymmetric total synthesis of veraflorizine, peimine and peiminine
BibTeX
@misc{yamaguchi2026transitionstate,
title = {{Transition-State Steric Fields Capture Geometric Signatures Associated with Electronic Perturbations in Asymmetric Catalysis}},
author = {Shigeru Yamaguchi},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009870/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009870/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Transition-State Steric Fields Capture Geometric Signatures Associated with Electronic Perturbations in Asymmetric Catalysis
AU - Shigeru Yamaguchi
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009870/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009870/v1
AB - In data analysis of molecular catalysis, molecular shape can be represented by voxel descriptors generated by mapping molecular structures onto a three-dimensional grid according to atomic van der Waals radii. Such voxel representations of molecular shape can be treated as steric molecular fields and are generally used as steric descriptors. However, because electronic perturbations can lead to systematic changes in molecular geometry, steric fields constructed from transition-state (TS) structures may also capture geometric signatures. We therefore examined whether steric fields derived from TS geometries can capture such structural changes associated with electronic perturbations in asymmetric catalysis. Using DFT-calculated TS structures from three asymmetric Michael addition systems, we generated two voxel-based molecular-field representations, steric fields and NPA-charge fields, for the major and minor TS pathways and used them to construct regression models with calculated enantioselectivity (ΔΔ G ‡ ) as the target variable. The resulting steric- and NPA-charge field models showed similar pathway-dependent trends in cross-validated coefficients of determination (q 2 ). The NPA-charge fields revealed distinct charge responses across the three reaction systems, and the associated changes in TS geometry were captured by the steric fields. These results indicate that TS-derived steric fields can encode not only molecular shape but also the geometric changes associated with electronic perturbations, providing simple and interpretable descriptors for data analysis in asymmetric catalysis.
ER -