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Stepwise Reduction of β-Trioxopyrrocorphins: Collapse of the Oxo-Induced Macrocycle Aromaticity.

Nivedita Chaudhri,Matthew J. Guberman‐Pfeffer,M. Zeller,C. Brückner

Published 2022 in Journal of Organic Chemistry

ABSTRACT

The diatropic ring current that characterizes the unexpectedly aromatic octaethyltrioxopyrrocorphins gets drastically reduced upon chemical reduction of one and particularly two ketone moieties. With increasing reduction, the chromophores containing one pyrrole, one/two pyrrolinone, and one/two pyrrolines become more similar to regular, nonmacrocycle-aromatic pyrrocorphins (hexahydroporphyrins). Single-crystal diffraction analysis shows the reduction products to be idealized planar. With increasing reduction, their UV-vis spectroscopic signatures are those of conjugated but nonaromatic oligopyrroles. Their diatropic ring currents, as assessed by 1H NMR spectroscopy, showed them to possess largely nonaromatic π-systems. Dihydroxylation of select β,β'-dioxobacteriochlorin and β,β'-dioxoisobacteriochlorins also resulted in the formation of equivalent mixed pyrrole/two pyrrolinone/pyrroline chromophores. Computations were able to reproduce the experimental trends of the diatropic ring currents and filled in the data for the regioisomers that could not be experimentally accessed. The work further highlights the electronic influence of the β-oxo-substituents and, more specifically, the origin of the aromaticity of the trioxopyrrocorphins. It also presents a series of chemically robust pyrrocorphins, a chromophore class for which many chemically very sensitive members have been reported.

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