A new approach for the copper-catalyzed functionalization of alkyl hydroperoxides with organosilicon compounds via in-situ-generated alkylsilyl peroxides

Using organosilicon compounds of the type Me 3 SiX (X = CN, N 3 , C n F 2n+1 , and halogens) and an amine base, alkylsilyl peroxides were generated in situ from the corresponding alkyl hydroperoxides . Subsequent in situ copper-catalyzed homolytic cleavage of the alkylsilyl peroxides afforded alkyl radicals, which were then trapped with a nucleophile X (X = CN, N 3 , C n F 2n+1 , and halogens) to furnish coupling products with new carbon–carbon, carbon–nitrogen, or carbon–halogen bonds in good to high yields. In addition, 1-(trimethylsilyl)morpholine can also be employed for the in-situ-generation of alkylsilyl peroxides, which are subsequently utilized for N-alkylation of amides, arylations , and borylations with high efficiency.