T. Shibata, T. Tsuji, S. Nishida
Mar 1, 1980
Citations
0
Influential Citations
5
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
The cycloadditions of dispiro[2.2.2.2]deca-4,9-diene (1) to isolated carbon-carbon multiple bonds have proceeded in two different modes, giving dispiro[2.2.4.2]dodeca-4,11-diene and tricyclo[6.4.0.03,6]dodeca-2,7-diene derivatives. Mono- and 1,2-disubstituted olefins and acetylenes gave the former adducts, whereas 1,1-disubstituted olefins gave the latter, as the major products. Evidence for the intermediacy of biradicals is provided. The observed difference in the mode of the cycloaddition is explained in terms of the stereoelectronic and/or steric effects in the transition state for the cyclization of the intermediate. The addition of 1 to tetracyanoethylene (TCNE) in wet acetone has proceeded via a zwitterionic intermediate(s), giving a 1:1:1 adduct of 1, TCNE, and water.