The Origin of Catalysis and Regioselectivity of Lewis Acid-Catalyzed Diels-Alder Reactions with Tropone**

Eveline H. Tiekink; Pascal Vermeeren; Trevor A. Hamlin

doi:10.1002/chem.202301223

The Origin of Catalysis and Regioselectivity of Lewis Acid-Catalyzed Diels-Alder Reactions with Tropone**

Eveline H. Tiekink, Pascal Vermeeren^*, Trevor A. Hamlin^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

We have studied the uncatalyzed and Lewis acid (LA)-catalyzed cycloaddition reaction between tropone and 1,1-dimethoxyethene using dispersion-corrected relativistic density functional theory (DFT). The LA catalysts BF₃, B(C₆H₅)₃, and B(C₆F₅)₃ efficiently accelerate both the competing [4+2] and [8+2] cycloaddition reactions by lowering the activation barrier up to 12 kcal mol⁻¹ compared to the uncatalyzed reaction. Our study reveals that the LA catalyst promotes both cycloaddition reaction pathways by LUMO-lowering catalysis and demonstrates that Pauli-lowering catalysis is not always the operative catalytic mechanism in cycloaddition reactions. Judicious choice of the LA catalyst can effectively impart regiocontrol of the cycloaddition: B(C₆H₅)₃ furnishes the [8+2] adduct while B(C₆F₅)₃ yields the [4+2] adduct. We discovered that the regioselectivity shift finds its origin in the ability of the LA to absorb distortion by adopting a trigonal pyramidal geometry around the boron atom.

Original language	English
Article number	e202301223
Pages (from-to)	1-7
Number of pages	7
Journal	Chemistry - A European Journal
Volume	29
Issue number	39
Early online date	20 Apr 2023
DOIs	https://doi.org/10.1002/chem.202301223
Publication status	Published - 11 Jul 2023

Bibliographical note

Funding Information:
This work was supported by the Netherlands Organization for Scientific Research (NWO). Quantum chemical calculations were performed at the SURFsara HPC center in Amsterdam. We thank Dr. Daniela Rodrigues Silva for insightful discussions.

Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Keywords

activation strain model
cycloaddition
density functional calculations
Lewis acids
regioselectivity

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title = "The Origin of Catalysis and Regioselectivity of Lewis Acid-Catalyzed Diels-Alder Reactions with Tropone**",

abstract = "We have studied the uncatalyzed and Lewis acid (LA)-catalyzed cycloaddition reaction between tropone and 1,1-dimethoxyethene using dispersion-corrected relativistic density functional theory (DFT). The LA catalysts BF3, B(C6H5)3, and B(C6F5)3 efficiently accelerate both the competing [4+2] and [8+2] cycloaddition reactions by lowering the activation barrier up to 12 kcal mol−1 compared to the uncatalyzed reaction. Our study reveals that the LA catalyst promotes both cycloaddition reaction pathways by LUMO-lowering catalysis and demonstrates that Pauli-lowering catalysis is not always the operative catalytic mechanism in cycloaddition reactions. Judicious choice of the LA catalyst can effectively impart regiocontrol of the cycloaddition: B(C6H5)3 furnishes the [8+2] adduct while B(C6F5)3 yields the [4+2] adduct. We discovered that the regioselectivity shift finds its origin in the ability of the LA to absorb distortion by adopting a trigonal pyramidal geometry around the boron atom.",

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The Origin of Catalysis and Regioselectivity of Lewis Acid-Catalyzed Diels-Alder Reactions with Tropone**

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Keywords

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