Palladium‐Catalyzed Aryl‐Carbamoylation of Alkene‐Tethered Carbamoyl Chlorides: Access to Diverse Aryl‐Functionalized Oxindoles

Abstract

Utilizing a palladium-catalyzed cascade strategy, we have developed an intermolecular aryl-carbamoylation of unactivated alkenes under mild conditions, allowing for facile access to diverse aryl-functionalized oxindoles from alkene-tethered carbamoyl chlorides in moderate to good yields.

Convenient Synthesis of Thioester‐Substituted Oxindoles by Palladium‐Catalyzed Thiocarbonylative Cyclization with Sulfonyl Chlorides as the Sulfur Source

“…[ 4 ] Not surprisingly, transition‐metal‐catalyzed cyclization/carbonylation reactions have been successfully explored for the construction of functionalized oxindoles. [ 5 ] Among these reactions, the incorporation of thioesters into oxindoles has drawn much attention, because thioester moieties have been recognized as a type of potent compound with distinctive chemical properties in life science and synthetic chemistry. [ 6‐7 ] However, reports on the preparation of thioester‐substituted oxindoles are limited.…”

“…Recently, Sun and co‐workers reported a nickel‐catalyzed reductive thioesterification of alkenes through a thioester molecule transfer reaction. [ 5d ] The exploration of more routes for the construction of thioester‐substituted oxindoles is of great interest.…”

Three-Component Visible-Light-Induced Palladium-Catalyzed 1,2-Alkyl Carbamoylation/Cyanation of Alkenes

“…Particularly attractive could be the 1,2-alkyl carbamoylation of alkenes, which would enable access to synthetically important amides, the prevalent structural motifs found in pharmaceuticals, biological molecules, and polymeric materials . Along this line, the two-component intramolecular annulative approach of alkyl-carbamoylation has been reported, but the process is substantially limited to carbamoyl-tethered alkenes, furnishing cyclic amides (Scheme b). To the best of our knowledge, no general methodology for the overall three-component alkyl carbamoylation has been developed.…”

“…Recently, visible-light-induced palladium catalysis has become an emerging field of study . We and others demonstrated that hybrid palladium C­(sp)-centered radical species, generated through the cleavage of C–X (X = halide, CO 2 NPhth) bonds in the presence of a photoexcited Pd(0) complex, enable desaturation, alkyl Heck, and other transformations …”

“…Inspired by the synthesis of ketenimines via free radical additions to isocyanides and a new mild and general visible-light-induced method for generation of radical species, we hypothesized an approach to ketenimines via an addition of hybrid palladium C­(sp)-centered radical species to isocyanides.…”