The Technology of Functionalized Tertiary-alkylations by Using the Reaction Field Near Copper Center

Abstract

The reaction of a copper salt and an α-bromocarbonyl compound, which is a great initiator for atom-transfer radical polymerizations or re-oxidant for low valent metal species, produces an α-radical species. But there are a few reports on tertiary-alkylations by using α-bromocarbonyl compounds as a tertiary-alkyl source. Although alkylation is important and fundamental chemistry in organic chemistry, tertiary-alkylation is still recognized as a challenging reaction. In our continuous studies on α-bromocarbonyl chemistry for tertiary-alkylation, we have established the Cu-catalyzed reaction systems including, A) tert-alkylative substitution reactions, B) formal cycloaddition reactions, C) cross-coupling type reactions, and D) divergent reaction. In this manuscript, I will introduce our methodology to control α-radical species in the presence of copper catalyst to realize diverse reactions to synthesize tertiary-alkylated olefins and cyclic compounds, and cross-coupling type reaction to load fluorine atom and amino groups.