Computational insights on the origin of enantioselectivity in reactions with diarylprolinol silyl ether catalysts <i>via</i> a radical pathway

Lam, Ching Ching; Goodman, Jonathan M.

doi:10.1039/d2qo00354f

Cited by 5 publications

(7 citation statements)

References 39 publications

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“…CONFPASS was used to assist the DFT re-optimizations of force field structures with confidence that key stable structures are obtained at a reduced computational cost (). 47,48 The default setting was used for generating the priority list for re-optimizing conformers. On average, we are more than 87% confident that the global minimum structure has been obtained after re-optimizing less than 37% of the conformers from the conformational searching output file (ESI Section 1.D†).…”

Section: Methodsmentioning

confidence: 99%

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

Lam,

Goodman

2023

Chem. Sci.

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Section: Methodsmentioning

confidence: 99%

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

Lam,

Goodman

2023

Chem. Sci.

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“…CONFPASS was used to assist the DFT re-optimizations of force eld structures with condence that key stable structures are obtained at a reduced computational cost (https://github.com/Goodman-lab/CONFPASS). 47,48 Fig. 2 Chiral oxazaborolidinium ion (COBI) catalysed reactions between aldehyde and diazo compounds.…”

Section: Methodsmentioning

confidence: 99%

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

Lam

Goodman

2023

Preprint

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The selectivity in a group of oxazaborolidinium ion-catalysed reactions between aldehyde and diazo compounds cannot be explained using transition state theory. VRAI-selectivity, developed to predict the outcome of dynamically controlled reactions, can account for both the chemo- and the stereo-selectivity in these reactions, which are controlled by reaction dynamics. Subtle modifications to the substrate or catalyst substituents alter the potential energy surface, leading to changes in predominant reaction pathways and altering the barriers to the major product when reaction dynamics are considered. In addition, this study suggests an explanation for the mysterious inversion of enantioselectivity resulting from the inclusion of an ortho iPrO group in the catalyst.

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“…Merz and co-workers have developed AutoGraph, which clusters conformers and produces conformational graphs for metabolites, such as oxidized nicotinamide adenine dinucleotide . We previously built an automated pipeline to select representative conformers for DFT re-optimizations using a conformation labeling system based on dihedral angle values specifically aimed at studying the reactivity of diarylprolinol silyl ether catalysts . CONFPASS builds on our earlier approach to generate a general pipeline for diverse organic structures.…”

Section: Introductionmentioning

confidence: 99%

“… 28 We previously built an automated pipeline to select representative conformers for DFT re-optimizations using a conformation labeling system based on dihedral angle values specifically aimed at studying the reactivity of diarylprolinol silyl ether catalysts. 29 CONFPASS builds on our earlier approach to generate a general pipeline for diverse organic structures.…”

Section: Introductionmentioning

confidence: 99%

CONFPASS: Fast DFT Re-Optimizations of Structures from Conformation Searches

Lam

Goodman

2023

J. Chem. Inf. Model.

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CONFPASS (Conformer Prioritizations and Analysis for DFT re-optimizations) has been developed to extract dihedral angle descriptors from conformational searching outputs, perform clustering, and return a priority list for density functional theory (DFT) re-optimizations. Evaluations were conducted with DFT data of the conformers for 150 structurally diverse molecules, most of which are flexible. CONFPASS gives a confidence estimate that the global minimum structure has been found, and based on our dataset, we can have 90% confidence after optimizing half of the FF structures. Re-optimizing conformers in order of the FF energy often generates duplicate results; using CONFPASS, the duplication rate is reduced by a factor of 2 for the first 30% of the re-optimizations, which include the global minimum structure about 80% of the time.

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Computational insights on the origin of enantioselectivity in reactions with diarylprolinol silyl ether catalysts via a radical pathway

Abstract: The stereoselective reaction of 1,4-dicarbonyls with diarylprolinol silyl ether catalysts was studied with force field and density functional theory calculations. A robust procedure has been developed for computational investigations of...

Cited by 5 publications

References 39 publications

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

Reaction dynamics as the missing puzzle piece: the origin of selectivity in oxazaborolidinium ion-catalysed reactions

CONFPASS: Fast DFT Re-Optimizations of Structures from Conformation Searches

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