On the Number of π-Electrons Involved in Stepwise Cycloaddition Reactions

TY - JOUR

T1 - On the Number of π-Electrons Involved in Stepwise Cycloaddition Reactions

AU - Inunnguaq Jessen, Nicolaj

AU - Izzo, Joseph A

AU - Modlinski, Marek S

AU - Bertuzzi, Giulio

AU - Anker Jørgensen, Karl

N1 - © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

PY - 2023/12/22

Y1 - 2023/12/22

N2 - The development of higher-order cycloadditions has mainly been restricted by the requisite usage of highly conjugated and reactive π-systems. Recent years have witnessed organocatalysis as a potent mediator for several of the challenges associated herein, rendering higher-order cycloadditions a legitimate option for achieving the selective construction of specific molecular scaffolds. These developments reinvigorate the efforts to try to understand the underlying principles for cycloadditions involving a higher number of π-electrons than the "classical" cycloadditions; how do we properly address the impact which the addition of further π-electrons have on the reactivity of a system? Herein, computational investigations of two model higher-order cycloaddition systems have been performed to try to provide insights on changes in energetic barriers induced by the presence of benzofusions in a position which is unobstructive to the reactivity. With experimental substantiation as support, these studies might open up for a discussion on whether the π-electrons of benzofused systems simply act as spectator electrons, or play a tangible role on the observed reactivity to an extent where a distinct nomenclature is meritable.

AB - The development of higher-order cycloadditions has mainly been restricted by the requisite usage of highly conjugated and reactive π-systems. Recent years have witnessed organocatalysis as a potent mediator for several of the challenges associated herein, rendering higher-order cycloadditions a legitimate option for achieving the selective construction of specific molecular scaffolds. These developments reinvigorate the efforts to try to understand the underlying principles for cycloadditions involving a higher number of π-electrons than the "classical" cycloadditions; how do we properly address the impact which the addition of further π-electrons have on the reactivity of a system? Herein, computational investigations of two model higher-order cycloaddition systems have been performed to try to provide insights on changes in energetic barriers induced by the presence of benzofusions in a position which is unobstructive to the reactivity. With experimental substantiation as support, these studies might open up for a discussion on whether the π-electrons of benzofused systems simply act as spectator electrons, or play a tangible role on the observed reactivity to an extent where a distinct nomenclature is meritable.

KW - DFT calculations

KW - cycloaddition

KW - mechanism

KW - reactivity

UR - http://www.scopus.com/inward/record.url?scp=85175630731&partnerID=8YFLogxK

U2 - 10.1002/chem.202303299

DO - 10.1002/chem.202303299

M3 - Journal article

C2 - 37851861

SN - 0947-6539

VL - 29

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 72

M1 - e202303299

ER -