Advanced Synthesis and Catalysis p. 2076 - 2089 (2017)
Update date:2022-08-17
Topics:
Sreenilayam, Gopeekrishnan
Moore, Eric J.
Steck, Viktoria
Fasan, Rudi
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 first-sphere coordination residue 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 the metal center, its oxidation state and first-sphere coordination environment on the catalytic activity, stereoselectivity, and/or oxygen tolerance of these artificial metalloenzymes. In addition, myoglobin variants incorporating manganese- or cobalt-porphyrins were found capable of catalyzing an intermolecular carbene C–H insertion reaction involving phthalan and ethyl α-diazoacetate, a reaction not supported by iron-based myoglobins and previously accessed only using iridium-based (bio)catalysts. These studies demonstrate how modification of the metalloporphyrin cofactor environment provides a viable and promising strategy to enhance the catalytic properties and extend the reaction scope of myoglobin-based carbene transfer catalysts. (Figure presented.).
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Doi:10.1007/BF00473931
(1992)Doi:10.1016/j.tetlet.2016.12.011
(2017)Doi:10.1021/np800453t
(2008)Doi:10.1021/j100365a040
(1990)Doi:10.1128/AAC.39.10.2304
(1995)Doi:10.1023/B:RACH.0000039116.09002.c8
(2004)