Hexachloroacetone as a precursor for a tetrachloro-substituted oxyallyl intermediate: [4+3] cycloaddition to cyclic 1,3-dienes.
The enol phosphate 2,2-dichloro-1-(trichloromethyl)ethenyl diethyl phosphate (1), easily available by a Perkow reaction between hexachloroacetone and triethyl phosphite, reacts with sodium trifluoroethoxide/trifluoroethanol in the presence of cyclic 5-membered 1,3-dienes to furnish alpha,alpha,alpha',alpha'-tetrachloro-substituted[3.2.1]bicyclic ketones 2. A [4+3] cycloaddition of a tetrachloro-oxyallyl intermediate is postulated.
Föhlisch
Baldur
B
Institut für Organische Chemie der Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. baldur.foehlisch@po.uni-stuttgart.de
Reiner
Stefan
S
D000096:Acetone / Q000031:analogs & derivatives* / Q000737:chemistry; D000498:Allyl Compounds / Q000737:chemistry*; D003500:Cyclization; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D015394:Molecular Structure
D000498:Allyl Compounds; D006844:Hydrocarbons, Cyclic; D007659:Ketones; D000096:Acetone; C032052:hexachloroacetone