Synthesis of Benzylic Quaternary Centers via Arylation with Aryl(TMP)iodonium Salts

Abstract

Benzylic quaternary centers are important molecular scaffolds, but their synthesis via the arylation of tertiary malonates remains underdeveloped. Herein, we exploit the metal-like reactivity of diaryliodonium salts to realize this transformation. Design of experiment (DoE) is used to discover mild conditions with a broad scope of aryl electrophiles in high yields, including the coupling of electron-rich aryl rings. Telescoping diaryliodonium synthesis and C–C coupling into a one-pot sequence opens a new possibility for C–C coupling with aryl iodides.