A cobalt-catalyzed C−H carbonylation of naphthylamides for the synthesis of benzo[cd]indol-2(1H)-one scaffolds has been developed. The reaction employs a traceless directing group and uses benzene-1,3,5-triyl triormate as the CO source, affording various free (NH)-benzo[cd]indol-2(1H)-ones in moderate to high yields (up to 88%). Using this protocol, the total synthesis of BET bromodomain inhibitors A and B was accomplished as well.

A palladium‐catalyzed carbonylative procedure for the synthesis of unsymmetrical ureas has been developed. This one‐pot one‐step cascade procedure is consisted by three individual processes: carbonylation, Curtius rearrangement, and nucleophilic addition. A series of unsymmetrical ureas were prepared from easily available aryl iodides and amines in moderate to excellent yields. This procedure provides a convenient and practical approach for unsymmetrical urea synthesis.magnified image

A procedure on palladium-catalyzed selective aminocarbonylation of styrenes with nitroarenes for the synthesis of α,β-unsaturated amides has been developed. A range of substituted α,β-unsaturated amides were synthesized in moderate to good yields. Interestingly, nitroarenes act as both a nitrogen source and oxidant, and Mo(CO) acts as a solid CO source and reductant in this catalytic system.

An ew procedure on palladium-catalyzedc arbonylative cyclization of N-(2-pyridyl)sulfonyl (N-SO 2 Py)-2iodoanilines with terminal alkenes has been developed for the rapid construction of dihydroquinolin-4(1H)-ones caffolds. Enabled by the chelatingg roup and using benzene-1,3,5-triyl triformate (TFBen) as the CO source, both aromatic and aliphatic alkenes were smoothly transformed into the corresponding 2,3-dihydroquinolin-4(1H)-ones in good yields with excellent regioselectivities. Notably,t he reaction of aromatic alkenes produces 2-aryl-2,3-dihydroquinolin-4(1H)-ones, while 3-alkyl-2,3-dihydroquinolin-4(1H)-ones were obtained when aliphatic alkenes were used. This protocol has been appliedi nt he synthesiso f antitumora gent A as well. Scheme3.Removal of the N-SO 2 Py directing group. Scheme4.Synthesis of the antitumoragent A. Scheme5.Preliminarymechanistic studies. Scheme6.Plausible mechanism.