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- Title
Diverged Plant Terpene Synthases Reroute the Carbocation Cyclization Path towards the Formation of Unprecedented 6/11/5 and 6/6/7/5 Sesterterpene Scaffolds.
- Authors
Huang, Ancheng C.; Osbourn, Anne; Hong, Young J.; Tantillo, Dean J.; Bond, Andrew D.
- Abstract
Abstract: Sesterterpenoids are a relatively rare class of plant terpenes. Sesterterpene synthase (STS)‐mediated cyclization of the linear C25 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.
- Subjects
TERPENES; CARBOCATIONS; RING formation (Chemistry); QUANTUM chemistry; BIOSYNTHESIS; NATURAL products
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 5, p1305
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201711444