Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 45, Pages 15190-15193Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b10077
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Funding
- North Carolina State University
- Carnegie Mellon University
- National Institutes of Health [GM127588]
- U.S. DOE [DE-FG02-02ER15354]
- NIH [RR023614]
- NSF [CHE-0840501]
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM127588] Funding Source: NIH RePORTER
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Installation of olefins into molecules is a key transformation in organic synthesis. The recently discovered decarboxylation-assisted olefination in the biosynthesis of rhabduscin by a mononuclear non-heme iron enzyme (P(center dot)IsnB) represents a novel approach in olefin construction. This method is commonly employed in natural product biosynthesis. Herein, we demonstrate that a ferryl intermediate is used for C-H activation at the benzylic position of the substrate. We further establish that P(center dot)IsnB reactivity can be switched from olefination to hydroxylation using electron-withdrawing groups appended on the phenyl moiety of the analogues. These experimental observations imply that a pathway involving an initial C-H activation followed by a benzylic carbocation species or by electron transfer coupled beta-scission is likely utilized to complete C=C bond formation.
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