Alkylation of remote non-activated δ-carbon atoms: Addition of δ-carbon radicals, generated by 1,5-hydrogen transfer in alkoxy radical intermediates, to activated olefins

✍ Scribed by Goran Petrović; Živorad Čeković

• Publisher: Elsevier Science
• Year: 1999
• Tongue: French
• Weight: 940 KB
• Volume: 55
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(98)01110-7

✦ Synopsis

A free radical introduction of a functionalized alkyl chain onto remote non-activated 8-carbon atoms (Michael type alkylation) has been achieved Photolysis of suitable alkyl nitrites involves generation of 8-alkyl radicals and in the presence of radicophilic olefins, intermolecular addition takes place and affords 8-alkylated products in 36-80% yields. 8-Alkylation is also achieved in the reaction of alkyl benzenesulfenates with tributyltin hydride (TBTH), in the presence of activated olefins and introduction of a :unctionalized alkyl chain involves alkoxy and 8-carbon radicals. Products with functionalized alkyl chains were obtained in 36-86% yields. 8-Alkylation of alkyl benzenesulfenates also occurs in the reaction with hexabutylditin in the presence of activated olefins.