Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis

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

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.

Citation

Tang, B., Simion, R., & Paton, R. S. (in press). Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis. SYNLETT, 26(4), https://doi.org/10.1055/s-0034-1379893

• Journal Article Type: Article
• Acceptance Date: Jan 14, 2015
• Online Publication Date: Feb 9, 2015
• Deposit Date: Oct 19, 2017
• Journal: Synlett
• Print ISSN: 0936-5214
• Electronic ISSN: 1437-2096
• Publisher: Thieme Publishing
• Peer Reviewed: Peer Reviewed
• Volume: 26
• Issue: 4
• DOI: https://doi.org/10.1055/s-0034-1379893
• Keywords: biosynthesis; concerted; cyclization; DFT; transition states
• Public URL: https://nottingham-repository.worktribe.com/output/745277
• Publisher URL: https://www.thieme-connect.de/DOI/DOI?10.1055/s-0034-1379893
• Contract Date: Oct 18, 2017