Ir-Catalyzed Atroposelective Desymmetrization of Heterobiaryls: Hydroarylation of Vinyl Ethers and Bicycloalkenes

Indium-catalyzed intramolecular hydroarylation of aryl propargyl ethers.

Indium(III) halides catalyze efficiently the intramolecular hydroarylation (IMHA) of aryl propargyl ethers. The reaction proceeds regioselectively with terminal and internal alkynes bearing electron-rich and electron-deficient substituents in the benzenes and alkynes affording only the 6-endo dig cyclization product. Additionally, a sequential indium-catalyzed IMHA and palladium-catalyzed Sonog...

Mechanism of iridium-catalysed branched-selective hydroarylation of vinyl ethers: a computational study.

The iridium-catalysed branched-selective hydroarylation of vinyl ethers represents a rare example of the branched-selective hydroarylation involving the non-styrene-type alkenes. Herein, we report our DFT calculations on the mechanism of this reaction. The results show that after C-H oxidative addition, instead of the widely accepted Chalk-Harrod type mechanism, the branched-selective hydroaryl...

Desymmetrization of cyclic olefins via asymmetric Heck reaction and hydroarylation.

An asymmetric Heck reaction allows desymmetrization of substituted cyclic olefins in high dr and ee. A bisphosphine oxide is uniquely stereoselective for this purpose. Desymmetrization of bicyclic olefins via hydroarylation can also be realized in high ee.

Formation of enamides via palladium(II)-catalyzed vinyl transfer from vinyl ethers to nitrogen nucleophiles.

Palladium(II) complexes catalyze the formation of enamides via the formal cross-coupling reaction between nitrogen nucleophiles and vinyl ethers. These vinyl transfer reactions proceed in good yields with amide, carbamate, and sulfonamide nucleophiles, and the optimal catalyst is (DPP)Pd(OCOCF(3))(2) (DPP = 4,7-diphenyl-1,10-phenanthroline). [reaction: see text]

Sequential In-catalyzed intramolecular hydroarylation and Pd-catalyzed cross-coupling reactions using bromopropargyl aryl ethers and amines†