Recent advances in transition metal-catalyzed reactions of carbamoyl chlorides

Abstract

The development of carbamoyl chlorides as synthons for various amide-containing molecules and heterocycles have been summarized and discussed in this review article. Carbamoyl chlorides can participate in a diverse range...

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

“…[4] In this context, alkene-tethered carbamoyl chlorides were recognized as a type of useful starting material to realize difunctionalization. [5] Efforts disclosed respectively by the groups of Tong, [6] Lautens, [7] Wang, [8] Chen and Qu [9] enabled carbamoyl-functionalization of pendant alkenes, leading to the synthesis of various functionalized oxindoles in one step manner. Moreover, many asymmetric versions have been developed with excellent stereoselectivities.…”

Nickel-Catalyzed Asymmetric Reductive Dicarbamoylation of Alkenes

“…Intramolecular Heck-type migratory insertion of a pendant olefinic unit into a chiral carbo-metal species constitutes the key enantiodiscriminating step for numerous transition metal-catalyzed asymmetric cyclizations . Although carbamoyl (pseudo)­halides have been known as carbamoylating agents for olefin difunctionalization over decades, the asymmetric variants are still scarce. , In 2008, Takemoto et al. reported the first enantioselective version of olefin carbamoylation utilizing cyanoformamides as the precursors under the catalysis of a chiral palladium complex (Scheme A, eq 1) .…”

Catalytic Desymmetric Dicarbofunctionalization of Unactivated Alkenes

“…Pyrrolidinones are among the most privileged scaffolds, widely existing in an array of biologically active natural products and pharmaceuticals [15] . Recently, transition metal‐catalyzed enantioselective transformation of stable carbamoyl chloride represents a complementary protocol for the rapid construction of the lactam scaffold [16] . Particularly, Wang reported the Ni/photoredox‐cocatalyzed asymmetric acyl‐carbamoylation and Ni‐catalyzed asymmetric reductive carbo‐carbamoylation of 1,1‐disubstituted alkenes to afford the oxindol skeleton bearing the quaternary stereogenic center [13f,h] .…”