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Synthesis, characterization and reactivity of complex tricyclic oxonium ions, proposed intermediates in natural product biosynthesis

Abstract:
Reactive intermediates frequently play significant roles in the biosynthesis of numerous classes of natural products although the direct observation of these biosynthetically relevant species is rare. We present here direct evidence for the existence of complex, thermally unstable, tricyclic oxonium ions that have been postulated as key reactive intermediates in the biosyn-thesis of numerous halogenated natural products from Laurencia species. Evidence for their existence comes from full characterization of these oxonium ions by low temperature NMR spectroscopy supported by DFT calculations, coupled with the direct generation of ten natural products on exposure of the oxonium ions to various nucleophiles.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/jacs.9b07438

Authors


More by this author
Institution:
University of Oxford
Department:
Chemistry
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Organic Chemistry
Oxford college:
St Hilda's College
Role:
Author
ORCID:
0000-0002-0104-4166
More by this author
Institution:
University of Oxford
Department:
Chemistry
Sub department:
Organic Chemistry
Oxford college:
Somerville College
Role:
Author


Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society More from this journal
Volume:
141
Issue:
40
Pages:
15951-15962
Publication date:
2019-09-27
Acceptance date:
2019-09-08
DOI:
EISSN:
1520-5126
ISSN:
0002-7863


Language:
English
Keywords:
Pubs id:
pubs:1052637
UUID:
uuid:0188aa06-1672-434d-a33b-9c6862ff937a
Local pid:
pubs:1052637
Source identifiers:
1052637
Deposit date:
2019-09-13

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