Cited by 23Chemical Reactions and MechanismsRadical Photochemical ReactionsOrganic Chemistry Cycloaddition Reactions

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

Adam, Waldemar, Kliem, Ulrike, Lucchini, Vittorio·1988·Liebigs Annalen der Chemie

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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Crossref · 10.1002/jlac.198819880909

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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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