Preparative UV‐VIS laser photochemistry: Photocycloadditions of methylenelactones with benzophenone and p‐benzoquinone. Oxygen trapping of paterno‐Büchi triplet 1,4‐diradicals as model reactions for quinghaosu‐type 1,2,4‐trioxanes
Abstract
The UV‐VIS laser irradiation of 4‐penten‐4‐olide (1) with benzophenone (BP) or with p‐benzoquinone (BQ) under an argon atmosphere afforded the acetal‐type oxetanes 2‐BP and 2‐BQ, respectively. Only for BP was the oxetane regioisomer 3‐BP obtained, actually as major product, while 3‐BQ appears to be photolabile under VIS‐laser photolysis conditions and thus does not accumulate in sufficient amounts for detection. Under an oxygen atmosphere, besides these oxetane products also the 1,2,4‐trioxanes 5‐PB and 5‐BQ, the oxygen trapping products of the intermediary preoxetane triplet diradicals 12, were isolated and fully characterized. These results demonstrate that spirolactone‐type 1,2,4‐trioxanes as quinghaosu analogues are accessible via trapping of Paterno‐Büchi triplet 1,4‐diradicals by molecular oxygen. In the case of diketene as enol‐lactone partner, the Paterno‐Büchi reaction with BQ gave a complex product mixture even under an argon atmosphere, leading to the oxetane 6 as major product, and the spirocyclobutanone 7 and spirobioxetane 8 as minor products. Under an oxygen atmosphere also the spiroacetal 9 was obtained, but no trioxanes (oxygen trapping) could be detected in this VIS‐laser photolysis.
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In vitro experiments have shown that 481 can undergo spontaneous conversion to a transient enol as proposed in step ii).
“These in vitro experiments have shown that 481 can indeed undergo sponataneous conversion to a transient enol as proposed in step ii) of Scheme 11 [204,238,243,302,303]”
From The Biosynthesis of Artemisinin (Qinghaosu) and the Phytochemistry of Artemisia annua L. (Qinghao) (2010) · cites this paper as [303]
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- Authors
- Adam, W., Kliem, U., & Lucchini, V.
- Affiliations
- University of Würzburg (DE)
- University of Padua (IT)
- Corresponding author
- Adam, Waldemar
- Venue
- Liebigs Annalen der Chemie
- Publisher
- Wiley
- Published
- 1988-09-14
- Volume
- 1988
- Issue
- 9
- Pages
- 869-875
- ISSN
- 0170-2041 (ISSN-L)
- OpenAlex
- W2122554114
- Cited by
- 23
- References
- 22
- Citations by year
- 2024: 1 · 2023: 1 · 2021: 1 · 2019: 2 · 2016: 1 · 2014: 1 · 2013: 1 · 2012: 1
- FWCI
- 2.48
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Liebigs Annalen der Chemie (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Chemical Reactions and Mechanisms
- Physical Sciences › Chemistry › Organic Chemistry › Radical Photochemical Reactions
- Physical Sciences › Chemistry › Organic Chemistry › Organic Chemistry Cycloaddition Reactions
- Keywords
- benzophenone, p-benzoquinone, photocycloaddition, oxetanes, 1,2,4-trioxanes, Paternò-Büchi reaction, oxygen trapping, spiroacetals, diketene, spirolactones
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