Redirecting a Diels–Alder Reaction toward (2 + 2)-Cycloaddition

Panova, Maria V.; Medvedev, Michael G.; Mar’yasov, M. A.; Lyssenko, Konstantin А.; Насакин, О. Е.

doi:10.1021/acs.joc.0c02386

Cited by 5 publications

(3 citation statements)

References 47 publications

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“…For example, the widely studied and utilized Diels-Alder [4+2] cycloaddition reaction has recently been found to compete with the [2+2] cycloaddition. 2,3 In a previous paper, 4 we investigated the [3+2] cycloaddition of O 3 (ozone), SO 2 (sulfur dioxide), CH 2 OO (formaldehyde oxide, Criegee radical), CH 2 SO (sulfine) and CH 2 SCH 2 (thioformaldehyde S-methylide) to ethylene and acetylene, in order to understand how the mechanism of pericyclic processes, like 1,3-dipolar cycloadditions, is influenced not only by the nature of the substituents, but also by the kind and number of heteroatoms in the 1,3-dipole. In this work, we extend the investigation to all the reaction steps involved in the different types of cycloaddition reactions between sulfur dioxide and acetylene.…”

Section: Introductionmentioning

confidence: 99%

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A new chapter in the never ending story of cycloadditions: The puzzling case of SO₂ and acetylene

Salta,

Ventura,

Rais

et al. 2024

J Comput Chem

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A comprehensive study of the different classes of cycloaddition reactions ([3+2], [2+2], and [2+1]) of SO2 to acetylene and ethylene has been performed using density functional theory (DFT) and composite wavefunction methods. The [3+2] cycloaddition reaction, that was previously explored in the context of the cycloaddition of thioformaldehyde S‐methylide (TSM) to ethylene and acetylene, proceeds in a concerted way to the formation of stable heterocycles. In this paper, we extend our study to the [2+2] and [2+1] cycloadditions of SO2 to acetylene, which would produce 1,1‐oxathiete‐2‐oxide and thiirene‐1,1‐dioxide, respectively. One of the main conclusions is that cyclic 1,1‐oxathiete‐2‐oxide can open through a relatively easy breaking of the SO single bond and rearrange toward sulfinyl acetaldehyde (SA). The SA molecule can easily undergo several internal rearrangements, which eventually lead to sulfenic acid and sulfoxide derivatives of ethenone, 1,2,3‐dioxathiole, and CO plus sulfinylmethane. The most probable path, however, produces 2‐thioxoacetic acid, whose derivatives (or those of the corresponding acetate) are usually obtained by Willgerodt–Kindler‐type sulfuration of acetates. This product can in turn decompose, leading to the final products CO2 and H2CS. Comparison of this decomposition path with that of 2‐amino‐2‐thioxoacetic acid shows that the process occurs through different H‐transfer processes.

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Section: Introductionmentioning

confidence: 99%

“…Despite a large number of experimental and theoretical studies, some mechanistic aspects deserve further investigation. For example, the widely studied and utilized Diels–Alder [4+2] cycloaddition reaction has recently been found to compete with the [2+2] cycloaddition 2,3 …”

Section: Introductionmentioning

confidence: 99%

A new chapter in the never ending story of cycloadditions: The puzzling case of SO₂ and acetylene

Salta,

Ventura,

Rais

et al. 2024

J Comput Chem

View full text Add to dashboard Cite

show abstract

“…Under thermal conditions, concerted [2 + 2] cycloadditions are symmetry forbidden . But stepwise [2 + 2] cycloadditions can be achieved by stabilizing the formation of a diradical, , a zwitterionic , intermediate, or by metal complexation. , Ketenes and allenes have an additional orthogonal π-bond − and can form four membered rings via a diradical mechanism. Stepwise [2 + 2] cycloadditions involving halogenated alkenes, polarized double bonds, , and allyl carbocations also are known.…”

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confidence: 99%