Proton-coupled electron transfer of macrocyclic ring hydrogenation: The chlorinphlorin.
basic_science · Level V
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- Record sourced from PubMed, PMID 35533271.
- Also identified by DOI 10.1073/pnas.2122063119 and PMC identifier 9171799.
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Abstract
SignificanceThe chemical reduction of unsaturated bonds occurs by hydrogenation with H<sub>2</sub> as the reductant. Conversely, in biology, the unavailability of H<sub>2</sub> engenders the typical reduction of unsaturated bonds with electrons and protons from different cofactors, requiring olefin hydrogenation to occur by proton-coupled electron transfer (PCET). Moreover, the redox noninnocence of tetrapyrrole macrocycles furnishes unusual PCET intermediates, including the phlorin, which is an intermediate in tetrapyrrole ring reductions. Whereas the phlorin of a porphyrin is well established, the phlorin of a chlorin is enigmatic. By controlling the PCET reactivity of a chlorin, including the use of a hangman functionality to manage the proton transfer, the formation of a chlorinphlorin by PCET is realized, and the mechanism for its formation is defined.