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Direct meso ‐Alkynylation of Metalloporphyrins Through Gold Catalysis for Hemoprotein Engineering
Author(s) -
Nierth Alexander,
Marletta Michael A.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310145
Subject(s) - chemistry , alkyne , porphyrin , combinatorial chemistry , hemeprotein , fluorophore , heme , catalysis , cycloaddition , click chemistry , ligand (biochemistry) , reagent , cofactor , hypervalent molecule , photochemistry , organic chemistry , fluorescence , biochemistry , physics , receptor , quantum mechanics , enzyme
A method was developed for the direct functionalization of metalloporphyrins at the methine protons (meso positions) to yield asymmetric alkynylated derivatives by using gold catalysis and hypervalent iodine reagents. This single‐step procedure was applied to b ‐type heme and the product was incorporated into a gas‐sensor heme protein. The terminal alkyne allows fluorophore labeling through copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC). Hemoproteins with this type of engineered cofactor have several potential applications in labeling and imaging technologies. Additionally, the alkyne provides a handle for modulating porphyrin electron density, which affects cofactor redox potential and ligand affinity. This method will be helpful for investigating the chemistry of natural heme proteins and for designing artificial variants with altered properties and reactivities.