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Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis

Tang, Bencan; Simion, Robert; Paton, Robert S.

Authors

Bencan Tang bencan.tang@nottingham.edu.cn

Robert Simion

Robert S. Paton robert.paton@chem.ox.ac.uk



Abstract

The unique structure of furanocembranoid natural product bielschowskysin has provoked a number of biosynthetic hypotheses: quantum chemical calculations provide a means to assess the feasibility of postulated mechanisms in the construction of this unusual carbon skeleton. Calculations reveal that thermal closure is possible in water via an unusual concerted cyclobutane-forming transition state without the intervention of an enzyme. Photocycloaddition is computed to be extremely efficient, provided enol ether triplet sensitization can be achieved by an appropriate light source. The possible existence of a stable dicarbonyl intermediate presents a challenge for the thermal route, implicating a photochemical pathway in bielschowskysin biosynthesis.

Journal Article Type Article
Journal Synlett
Print ISSN 0936-5214
Electronic ISSN 1437-2096
Publisher Georg Thieme Verlag
Peer Reviewed Peer Reviewed
Volume 26
Issue 4
APA6 Citation Tang, B., Simion, R., & Paton, R. S. (in press). Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis. SYNLETT, 26(4), doi:10.1055/s-0034-1379893
DOI https://doi.org/10.1055/s-0034-1379893
Keywords biosynthesis; concerted; cyclization; DFT; transition states
Publisher URL https://www.thieme-connect.de/DOI/DOI?10.1055/s-0034-1379893
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf

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