The regioselective addition of aryl and aryldiazenyl substituents to olefinic substrates can be described as carbodiazenylation. In this report we present our final results relating to this unique type of radical functionalization reaction, which has now been developed into a convenient, versatile and highly effective synthetic method. Starting from an investigation into rate constants for the addition of aryl radicals to monosubstituted, non-activated olefins, this key step is shown to be both fast and selective in mixtures of dimethyl sulfoxide and water. The by-products obtained in earlier reactions reveal that the main complication of carbodiazenyl-

Allylation and vinylation of aryl radicals generated from aryl diazonium salts provides rapid and efficient access to chlorinated and brominated derivatives of styrene and allylbenzene. Allyl chlorides were found to be better substrates than bromides due to decreased halogen transfer. Donor- and acceptor-substituted diazonium salts are well tolerated. The products represent important precursors for numerous further transformations.

Alkenes Q 0083Allylation and Vinylation of Aryl Radicals Generated from Diazonium Salts. -The simple, rapid, and effective method affords allylbenzenes and styrene derivatives. The reaction with propargyl halides is also studied, but only poor yields of allenes are obtained [cf. (XII)]. -(HEINRICH*, M. R.; BLANK, O.; ULLRICH, D.; KIRSCHSTEIN, M.; J. Org. Chem. 72 (2007) 25, 9609-9616; Lehrstuhl Org. Chem.,

Azo compounds Q 0160 Radical Carbodiazenylation -A Convenient and Effective Method to AchieveCarboamination of Non-Activated Olefins. -An improved procedure for radical diazenylation of alkenes is presented. -(BLANK, O.; WETZEL, A.; ULLRICH, D.; HEINRICH*, M. R.; Eur.