Palladium-Catalyzed Carbonylative Multicomponent Fluoroalkylation of 1,3-Enynes: Concise Construction of Diverse Cyclic Compounds.

Multicomponent reactions, particularly those entailing four or more reagents, have presented a longstanding challenge due to the inherent complexities associated with balancing reactivity, selectivity, and compatibility. In this study, we describe a palladium-catalyzed multi-component fluoroalkylative carbonylation of 1,3-enynes. A series of products featuring three active functional groups-allene, fluoroalkyl, and carboxyl, were efficiently and selectively integrated in a single chemical operation. Furthermore, more intricate fluoroalkyl-substituted pyrimidinones can be constructed by simply altering the 1,3-bisnucleophilic reagent. This approach also provides a valuable strategy for the late-stage modification of naturally occurring molecules and concise construction of diverse cyclic compounds.

Palladium-Catalyzed Regioselective Carbonylation of 2-Trifluoromethyl-1,3-enynes to Multisubstituted Conjugated Dienes.

In this communication, a palladium-catalyzed regio- and stereoselective carbonylation of 2-trifluoromethyl-1,3-enynes to afford multisubstituted conjugated dienes has been realized. This protocol features excellent regio- and exclusive (E)-stereoselectivity and a broad substrate scope with both amines and alcohols as the suitable reaction partners and has shown promising functional group tolerance.

Palladium-Catalyzed Regio- and Stereoselective Hydroaminocarbonylation of Unsymmetrical Internal Alkynes toward α,ß-Unsaturated Amides.

α,ß-Unsaturated amides play a vital role in natural products, pharmaceuticals, organic synthesis, and functional materials. Herein, we disclosed a regio- and stereoselective hydroaminocarbonylation of unsymmetrical internal alkynes via palladium catalysis to synthesize α,ß-unsaturated amides. This protocol features excellent regio- and exclusive (E)-stereoselectivity, high atom and step-economy, broad substrate scope, and functional group tolerance.

Cobalt-Catalyzed Four-Component Carbonylation of Methylarenes with Ethylene and Alcohols.

Direct conversion of raw materials to fine chemicals is greatly economically influential. We developed a non-expensive cobalt-catalyzed multicomponent carbonylative reaction for the synthesis of γ-aryl carboxylic acid esters from readily available methylarene, ethylene, and CO, which are widely found in multiple FDA-approved drugs.

Palladium-Catalyzed Direct Dicarbonylation of Amines with Ethylene to Imides.

The selective and effective conversion of low-cost and simple bulk chemicals into high value-added products through catalytic strategy has a wide range of practical significance. Here, a palladium-catalyzed method for the direct and efficient dicarbonylation of amines with basic industrial feedstock ethylene to imide has been developed. Moderate to excellent yields of the desired imides can be produced from readily available amines in a straightforward manner.

Ligand-Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis.

A method for the regiodivergent and stereoselective hydrosilylation of the basic industrial feedstock isoprene with unactivated silanes has been developed using earth-abundant iron catalysts. The manipulation of regioselectivity relies on fine modification of the coordination geometry of the iron center. While a bidentate pyridine imine ligand promoted the formation of allylic silanes through 4,1-addition, selectivity for the 3,4-adduct homoallylic silanes was observed with a tridentate nitrogen ligand. Experimental studies and analysis were carried out to elucidate the reaction mechanism and the factors enabling manipulation of the regioselectivity. This study contributes to the art of regioselectivity control in alkene hydrofunctionalization.

Rhodium-catalyzed regio- and enantioselective allylic alkylation of pyrazol-5-ones with alkynes.

A rhodium-catalyzed asymmetric allylic alkylation of pyrazol-5-ones with internal alkynes is illustrated. In the presence of a chiral rhodium-hydride catalyst, functionalized heterocyclic products bearing an all-carbon quaternary stereogenic center were obtained in high yields with satisfactory enantioselectivities. This protocol also features good regiocontrol and a high atom economy without stoichiometric by-product formation.