Mn^I/Ag^I Relay Catalysis: Traceless Diazo‐Assisted C(sp²)–H/C(sp³)–H Coupling to β‐(Hetero)Aryl/Alkenyl Ketones

Abstract

An unprecedented Mn^I /Ag^I -relay-catalyzed C(sp² )-H/C(sp³ )-H coupling of (vinyl)arenes with α-diazoketones is reported, wherein the diazo group was exploited as a traceless auxiliary for control of regioselectivity. Challenging β-(hetero)aryl/alkenyl ketones were obtained through this operationally simple approach. The cascade process merges denitrogenation, carbene rearrangement, C-H activation, and hydroarylation/hydroalkenylation. The robustness of this method was demonstrated at preparative scale and applied to late-stage diversification of natural products.