期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 57, 期 5, 页码 1291-1295出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201711444
关键词
cyclization; natural products; quantum chemical calculations; sesterterpene biosynthesis; terpene synthases
资金
- National Institutes of Health Genome to Natural Products Network award [U101GM110699]
- European Commission Marie Sklodowska-Curie Individual Fellowship [H2020-MSCA-IF-EF-ST-702478-TRIGEM]
- UK Biotechnological and Biological Sciences Research Council (BBSRC) Institute Strategic Programme Grant Molecules from Nature [BB/P012523/1]
- John Innes Foundation
- US National Science Foundation [CHE-1565933, CHE030089 [XSEDE]]
- BBSRC [BBS/E/J/000PR9794, BBS/E/J/000PR9790, BB/L014130/1] Funding Source: UKRI
- Biotechnology and Biological Sciences Research Council [BBS/E/J/000PR9794, BBS/E/J/00000614, BBS/E/J/000PR9790] Funding Source: researchfish
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [U01GM110699] Funding Source: NIH RePORTER
Sesterterpenoids are a relatively rare class of plant terpenes. Sesterterpene synthase (STS)-mediated cyclization of the linear C-25 isoprenoid precursor geranylfarnesyl diphosphate (GFPP) defines sesterterpene scaffolds. So far only a very limited number of STSs have been characterized. The discovery of three new plant STSs is reported that produce a suite of sesterterpenes with unprecedented 6/11/5 and 6/6/7/5 fused ring systems when transiently co-expressed with a GFPP synthase in Nicotiana benthamiana. Structural elucidation, feeding experiments, and quantum chemical calculations suggest that these STSs catalyze an unusual cyclization path involving reprotonation, intramolecular 1,6 proton transfer, and concerted but asynchronous bicyclization events. The cyclization is diverted from those catalyzed by the characterized plant STSs by forming unified 15/5 bicyclic sesterterpene intermediates. Mutagenesis further revealed a conserved amino acid residue implicated in reprotonation.
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