Diels‐Alder Reactions of Tetradehydrodianthracene with Electron‐Rich Dienes
- 1 November 1996
- journal article
- Published by Wiley in European Journal of Organic Chemistry
- Vol. 1996 (11) , 1795-1800
- https://doi.org/10.1002/jlac.199619961113
Abstract
Tetradehydrodianthracene (TDDA; 1) reacts with electronrich dienes such as butadiene, cyclopentadiene and o‐quinodimethane under ambient conditions. Only 1:1 products 5–8 were observed even with a large excess of the diene and under drastic conditions (though two strained and highly pyramidalized double bonds are available). The enhanced reactivity of TDDA compared with its mono Diels‐Alder adducts is mainly due to the through‐bond and through‐space interaction of the two olefinic double bonds. During the cycloaddition one of the olefinic bonds in TDDA is converted into an extremely long C–C single bond (> 1.65 Å). Attempts to cleave the strained π‐bond thermochemically to form a diradical 13 afforded product 14a that was formed via a formal intramolecular homo 1,3‐sigmatropic shift.Keywords
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