Synthetic Applications of Homolytic Addition and Telomerisation Reactions of Bromine-Containing Addends with Unsaturated Compounds Containing Electron-Withdrawing Substituents

This paper summarises the recently reported data on reactions involving homolytic addition of bromine-containing electrophiles (polyhalomethanes, dibromo- and tribromocarboxylates, diethyl dibromomalonate) across electron-deficient double bonds (acrylic and crotonic systems, vinyl chloride) which proceed via cleavage of C-Br bonds. In particular, telomerisation reactions of this type are considered. Initiating agents, efficient in such reactions, are coordination compounds of polyvalent transition metals in combination with nucleophiles as cocatalysts. The reactions described open routes to bromine-containing compounds which are hardly accessible otherwise. 1. Introduction 2. Reactions of Acrylic Monomers with 2-Bromo- and 2,2-Dibromocarboxylates and with Methyl Tribromoacetate 3. Addition and Telomerisation Reactions of Acrylic Compounds with Bromine-Containing Polyhaloalkanes 4. Homolytic Addition of Bromine-Containing Addends to Alkenes with Internal Double Bonds 5. Step-Wise Telomerisation 6. Side Reactions