A Porphyrin-Based Molecular Cage Guided by Designed Local-Electric Field Is Highly Selective and Efficient

29 August 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The present work outlines a general methodology for designing efficient catalytic machineries that can easily be tweaked to meet the demands of the target reactions. This work utilizes a principle of the designed local electric field (LEF) as the driver for an efficient catalyst. It is demonstrated that by tweaking the LEF, we can catalyze the desired hydroxylation products with enantioselectivity that can be changed at will. Using computation tools, we caged a synthetic analog of heme porphyrin (HM1) and investigated the pharmaceutically relevant conversion of Tetralin to Tetralol, inside the modified supramolecular cage. The QM/MM calculations demonstrate a resulting catalytic efficiency with virtually absolute Pro-R selectivity for the tetralin hydroxylation. Our calculations show that the LEF of the supramolecular cage and HM1 exerts a strong electric field along the Fe—O reaction axis, which is the main driving force for enhanced reactivity. At the same time, the supramolecular cage applies a lateral LEF that regulates the enantioselectivity. We further demonstrate that swapping the charged/polar substitution in the supramolecular cage switches the lateral LEF which changes the enantioselectivity of hydroxylation from R to S.


Catalyst Design
Designed Electric Field
QM/MM calculations

Supplementary materials

Supplementary material
Coordinates, reaction profile, details methods etc


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