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Electrostatic Interactions in Asymmetric Organocatalysis.

Rajat Maji¹, Sharath Chandra Mallojjala¹, Steven E Wheeler¹

¹Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.

Accounts of Chemical Research

|July 6, 2023

Summary

This summary is machine-generated.

Quantum chemistry computations reveal electrostatic interactions are key to controlling reactivity and stereoselectivity in asymmetric organocatalysis. These insights guide catalyst design for more efficient and selective chemical reactions.

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Area of Science:

Computational chemistry
Asymmetric organocatalysis
Quantum chemistry

Background:

Electrostatic interactions are crucial in catalytic systems, influencing reactivity and stereoselectivity.
Quantifying electrostatic effects in transition states (TS) has been challenging, limiting their application.
Advances in computation and quantum chemistry now enable detailed atomic-level analysis.

Purpose of the Study:

To elucidate the pivotal roles of electrostatic interactions in organizing TS structures.
To demonstrate how these interactions direct reactivity and selectivity in asymmetric organocatalysis.
To provide a foundation in electrostatics and computational approaches for understanding these effects.

Main Methods:

State-of-the-art quantum chemical computations.
Analysis of electrostatic interactions in transition state (TS) structures.
Investigation across chiral phosphoric acid (CPA), N-heterocyclic carbene (NHC), and silylium ion catalysis.

Main Results:

CPA-catalyzed reactions (epoxide ring openings, oxetane desymmetrizations, dihydroquinazolinone synthesis) are directed by electrostatic stabilization of TS.
NHC-catalyzed kinetic resolutions show electrostatic stabilization of protons as the common selectivity driver.
Silylium ion-catalyzed Diels-Alder reactions utilize electrostatic interactions to guide endo:exo selectivity.

Conclusions:

Electrostatic interactions are fundamental in organizing transition states for reactivity and selectivity in asymmetric organocatalysis.
Computational chemistry provides powerful tools to understand and exploit these interactions.
Further computational efforts can enable the design of novel catalysts and reactions.