Cobalt-assisted α-activation of ketones. Their arylation and keto-enol equilibrium confined into a macrocycle

31 October 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

In this study, we explore the cobalt-mediated α-activation of ketones within modified porphyrin macrocycles, focusing on the arylation processes and the influence of macrocyclic confinement on keto-enol tautomerism. The activation of ketones such as acetone, butanone, 3-pentanone, and acetophenone and their possible transfer from a cobalt centre on the carbaporphyrin fragment results in the forming of new C(sp²)–C(sp³) bonds in confined macrocyclic environments of N-confused porphyrin and azuliporphyrin. Such modified ligands allow for following altered keto-enol equilibrium. They reversibly form unique structural motifs, azuleno[1,2-c]pyran and 2,4-dihydropyrano[3,4-c]pyrrole modulated by acid-base conditions and macrocyclic aromaticity. The coordination of a modified macrocycle to a rhodium(I) centre leads to a series of complexes with a final form with rhodium(III) in the cavity. The rhodium(III) centre cleaved the C(21)–C bond and transferred the acetone fragment back to the metal ion from the azulene fragment.

Keywords

carbaporphyrin
cobalt
ketone
azuliporphyrin
bond cleavage
keto-enol equilibrium
N-confused porphyrin
arylation
CH activation
paramagnetic
paramagnetic NMR
X-ray
molecular confinement

Supplementary materials

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Title
Cobalt-assisted α-activation of ketones. Their arylation and keto-enol equilibrium confined into a macrocycle
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