Angew Chem Int Ed Engl
Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
Published: September 2019
The selective functionalization of one C-H bond over others in nearly identical steric and electronic environments can facilitate the construction of complex molecules. We report site-selective functionalizations of C-H bonds, differentiated solely by remote substituents, catalyzed by artificial metalloenzymes (ArMs) that are generated from the combination of an evolvable P450 scaffold and an iridium-porphyrin cofactor. The generated systems catalyze the insertion of carbenes into the C-H bonds of a range of phthalan derivatives containing substituents that render the two methylene positions in each phthalan inequivalent. These reactions occur with site-selectivity ratios of up to 17.8:1 and, in most cases, with pairs of enzyme mutants that preferentially form each of the two constitutional isomers. This study demonstrates the potential of abiotic reactions catalyzed by metalloenzymes to functionalize C-H bonds with site selectivity that is difficult to achieve with small-molecule catalysts.
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http://dx.doi.org/10.1002/anie.201907460 | DOI Listing |
Org Lett
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Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, College of Chemistry & Chemical Engineering, Anhui University, Hefei, Anhui 230601, China.
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School of Electrical Engineering, Shandong University, Jinan 250061, China.
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California Institute for Quantitative Biosciences, University of California, Berkeley, CA 94720.
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Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States.
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