Multichromophoric Systems by Diels-Alder Reaction of Barrelene with o-Benzoquinones: Tetracyclo[6.2.2.23,6.02,7]tetradeca-9,11,13-triene-4,5-diones

• Published in: European journal of organic chemistry Vol. 1998; no. 11; pp. 2339 - 2348
• Main Authors: Behr, Jürgen, Braun, Ralf, Grimme, Stefan, Kummer, Matthias, Martin, Hans-Dieter, Mayer, Bernhard, Rubin, Mordecai B., Ruck, Christoph
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 01.11.1998; WILEY‐VCH Verlag GmbH; Wiley
• Subjects: Cage compounds; Chemistry; Chemistry, Organic; Cycloadditions; Density functional calculations; Photochemistry; Physical Sciences; Quinones; Science & Technology; PHOTOELECTRON-SPECTRA; MEDIUM RINGS; cycloadditions; BETA; density functional calculations; SPECTROSCOPY; MODELS; photochemistry; FRAGMENT; quinones; ELECTRON-TRANSFER EQUILIBRIA; cage compounds; AFFINITIES
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/(SICI)1099-0690(199811)1998:11<2339::AID-EJOC2339>3.0.CO;2-2

Thermal addition of o‐benzoquinones to barrelenes (bicyclo[2.2.2]octatrienes) produces tetracyclic trienediones of type 1. These multichromophoric molecules offer a plethora of photochemical reactions of which the most interesting are (1) rearrangement and bisdecarbonylation of the enedione chromophore and (2) [2π + 2π] intramolecular cycloaddition of the face‐to‐face double bonds. Theoretical methods (semiempirical as well as density functional) were also used to investigate the spin multiplicity diversity of these reactions. The diketone 7 (bicyclo[2.2.2]octa‐5,7‐diene‐2,3‐dione) was investigated using He(I) photoelectron spectroscopy.