Palladium-Catalyzed Heck Cyclization Research Articles

Palladium-Catalyzed Heck Cyclization with P(O)H Compounds to Construct Phosphinonyl-Azaindoline and -Azaoxindole Derivatives.

We report herein a concise method for the construction of phosphinonyl-azaindoline and -azaoxindole derivatives via a palladium-catalyzed cascade cyclization with P(O)H compounds. Various H-phosphonates, H-phosphinates, and aromatic secondary phosphine oxides are all tolerated under the reaction conditions. Furthermore, the phosphinonyl-azaindoline isomer families such as 7-, 5-, and 4-azaindolines could be synthesized in moderate to good yields.

Palladium-catalyzed Heck/aminocarbonylation of alkene-tethered carbamoyl chlorides with nitro compounds for the synthesis of carbamoyl-substituted oxindoles.

A straightforward and efficient approach for the synthesis of carbamoyl-substituted oxindoles has been developed via a palladium-catalyzed Heck cyclization and reductive aminocarbonylation reaction of alkene-tethered carbamoyl chlorides with nitro compounds. The reaction showed good compatibility toward versatile functional groups, and both nitroarenes and nitroalkanes were well tolerated. Using Mo(CO)6 as a solid CO source, without external reductants, a broad range of carbamoyl-substituted oxindoles were obtained in moderate to high yields.

Synthesis of Bridged Biaryl Atropisomers via Sequential Cu- and Pd-Catalyzed Asymmetric Ring Opening and Cyclization.

Bridged biaryl atropisomers are important units in bioactive molecules. A synthesis of lactone-bridged biaryl atropisomers was realized by a Cu-catalyzed asymmetric ring-opening/acyoxylation of cyclic diaryliodoniums, followed by a palladium-catalyzed diastereoselective cyclization. It was found that a catalytic amount of Cu(OTf)2 served as an additive to promote the palladium-catalyzed Heck cyclization.

Synthesis of Functionalized Alkylidene Indanes and Indanones through Tandem Phosphine-Palladium Catalysis.

Densely functionalized alkylidene indanes and indanones can be prepared efficiently in one pot, in high yields with good stereoselectivities (in some cases exclusively the Z-isomer), through a route involving phosphine-catalyzed Michael addition followed by palladium-catalyzed Heck cyclization. These transformations tolerate substrates bearing various substituents around the indane/indanone motif. Employing this technology, a concise formal synthesis of sulindac, a nonsteroidal anti-inflammatory drug, has been established.

Pd-catalyzed Heck cyclization and in situ hydrocarboxylation or hydromethenylation via a hydrogen borrowing strategy

A palladium-catalyzed Heck cyclization and in situ hydrocarboxylation reaction was developed using chloroform as a one-carbon elongation reagent.

New Efficient Synthesis of Pyrido[2,3-c]coumarin Derivatives by Palladium-Catalyzed Heck Cyclization

Tetrahydropyrido[2,3-c]coumarin derivatives were synthesized by intramolecular radical cyclization and Heck coupling. This method allowed the synthesis of the backbone of the Santiagonamine alkaloid.