Metal Substitution Modulates the Reactivity and Extends the Reaction Scope of Myoglobin Carbene Transfer Catalysts.

ABSTRACT: Engineered myoglobins have recently emerged as promising scaffolds for catalyzing carbene-mediated transformations. In this work, we investigated the effect of altering the metal center and its first-sphere coordination environment on the carbene transfer reactivity of myoglobin. To this end, we first established an efficient protocol for the recombinant expression of myoglobin variants incorporating metalloporphyrins with non-native metals, including second- and third-row transition metals (ruthenium, rhodium, iridium). Characterization of the cofactor-substituted myoglobin variants across three different carbene transfer reactions (cyclopropanation, N-H insertion, S-H insertion) revealed a major influence of the nature of metal center, its oxidation state and first-sphere coordination en

SUBMITTER: Sreenilayam G 

PROVIDER: S-EPMC5875932 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature