期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 21, 页码 6846-6879出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201807844
关键词
electrophilic cascades; natural products; nucleophilic cascades; pericyclic cascades; radical cascades
资金
- NIH [R01-AI047818]
Enzyme-mediated cascade reactions are widespread in biosynthesis. To facilitate comparison with the mechanistic categorizations of cascade reactions by synthetic chemists and delineate the common underlying chemistry, we discuss four types of enzymatic cascade reactions: those involving nucleophilic, electrophilic, pericyclic, and radical reactions. Two subtypes of enzymes that generate radical cascades exist at opposite ends of the oxygen abundance spectrum. Iron-based enzymes use O-2 to generate high valent iron-oxo species to homolyze unactivated C-H bonds in substrates to initiate skeletal rearrangements. At anaerobic end, enzymes reversibly cleave S-adenosylmethionine (SAM) to generate the 5 '-deoxyadenosyl radical as a powerful oxidant to initiate C-H bond homolysis in bound substrates. The latter enzymes are termed radical SAM enzymes. We categorize the former as thwarted oxygenases.
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