Enhancing Flavins Photochemical Activity in Hydrogen Atom Abstraction and Triplet Sensitization through Ring‐Contraction

Author:

Rehpenn Andreas1,Hindelang Stephan1,Truong Khai‐Nghi2ORCID,Pöthig Alexander1ORCID,Storch Golo1ORCID

Affiliation:

1. Technical University of Munich (TUM) School of Natural Sciences and Catalysis Research Center (CRC) Lichtenbergstr. 4 85747 Garching Germany

2. Rigaku Europe SE Hugenottenallee 167 63263 Neu-Isenburg Germany

Abstract

AbstractThe isoalloxazine heterocycle of flavin cofactors reacts with various nucleophiles to form covalent adducts with important functions in enzymes. Molecular flavin models allow for the characterization of such adducts and the study of their properties. A fascinating set of reactions occurs when flavins react with hydroxide base, which leads to imidazolonequinoxalines, ring‐contracted flavins, with so far unexplored activity. We report a systematic study of the photophysical properties of this new chromophore by absorption and emission spectroscopy as well as cyclic voltammetry. Excited, ring‐contracted flavins are significantly stronger hydrogen atom abstractors when compared to the parent flavins, which allowed the direct trifluoromethylthiolation of aliphatic methine positions (bond dissociation energy (BDE) of 400.8 kJ mol−1). In an orthogonal activity, their increased triplet energy (E(S0←T1)=244 kJ mol−1) made sensitized reactions possible which exceeded the power of standard flavins. Combining both properties, ring‐contracted flavin catalysts enabled the one‐pot, five‐step transformation of α‐tropolone into trans‐3,4‐disubstituted cyclopentanones. We envision this new class of flavin‐derived chromophores to open up new modes of reactivity that are currently impossible with unmodified flavins.

Funder

Fonds der Chemischen Industrie

Deutsche Forschungsgemeinschaft

Publisher

Wiley

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