Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 39, Pages 13954-13960Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201907460
Keywords
artificial metalloenzymes; biocatalysis; C-H functionalization; porphyrins; P450 enzymes
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Funding
- Office of Science, of the U.S. Department of Energy [DE-AC02-05CH11231]
- Pharmaron
- Shanghai Institute of Organic Chemistry (SIOC)
- NIH [F32-GM126652]
- Burroughs Welcome fund (PDEB)
- National Science Scholarship from the Singapore Agency for Science, Technology and Research
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
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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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