Naphthol radical couplings determine structural features and enantiomeric excess of dalesconols in Daldinia eschscholzii.
Nat Commun, 2012;3:1039.
Fang W[1], Ji S, Jiang N, Wang W, Zhao GY, Zhang S, Ge HM, Xu Q, Zhang AH, Zhang YL, Song YC, Zhang J, Tan RX
Affiliations
PMID: 22948821DOI: 10.1038/ncomms2031
Impact factor: 17.694
Abstract
Understanding how simple molecules are pieced together in organisms may aid biotechnological manipulation and synthetic approaches to complex natural products. The mantis-associated fungus Daldinia eschscholzii IFB-TL01 produces the unusually structured immunosuppressants (±)-dalesconols A and B, along with their congener (±)-dalesconol C, with the (-)-enantiomers in excess. Here we report that these structural and stereochemical peculiarities of dalesconols A-C are a result of promiscuous and atropselective couplings of radicals derived from 1,3,6,8-tetrahydroxynaphthalene, 1,3,8-trihydroxynaphthalene and 1,8-dihydroxynaphthalene. The observed (-)-enantiomeric excess is found to depend on the dominance of particular conformers of naphthol dimer intermediates, which are ligands of laccase.
MeSH terms
Dibenzocycloheptenes; Free Radicals; Naphthols; Polycyclic Aromatic Hydrocarbons; Stereoisomerism; Xylariales
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