Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis
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 th...
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| Format: | Article |
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Thieme
2015
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| Online Access: | https://eprints.nottingham.ac.uk/47353/ |
| _version_ | 1848797524197900288 |
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| author | Tang, Bencan Simion, Robert Paton, Robert S. |
| author_facet | Tang, Bencan Simion, Robert Paton, Robert S. |
| author_sort | Tang, Bencan |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T20:05:14Z |
| format | Article |
| id | nottingham-47353 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T20:05:14Z |
| publishDate | 2015 |
| publisher | Thieme |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-473532020-05-04T17:02:55Z https://eprints.nottingham.ac.uk/47353/ Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis Tang, Bencan Simion, Robert Paton, Robert S. 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. Thieme 2015-02-09 Article PeerReviewed Tang, Bencan, Simion, Robert and Paton, Robert S. (2015) Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis. Synlett, 26 (04). pp. 501-507. ISSN 1437-2096 biosynthesis; concerted; cyclization; DFT; transition states https://www.thieme-connect.de/DOI/DOI?10.1055/s-0034-1379893 doi:10.1055/s-0034-1379893 doi:10.1055/s-0034-1379893 |
| spellingShingle | biosynthesis; concerted; cyclization; DFT; transition states Tang, Bencan Simion, Robert Paton, Robert S. Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title | Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title_full | Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title_fullStr | Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title_full_unstemmed | Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title_short | Thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| title_sort | thermal and photochemical mechanisms for cyclobutane formation in bielschowskysin biosynthesis |
| topic | biosynthesis; concerted; cyclization; DFT; transition states |
| url | https://eprints.nottingham.ac.uk/47353/ https://eprints.nottingham.ac.uk/47353/ https://eprints.nottingham.ac.uk/47353/ |