Highly functionalized and stereocontrolled syntheses of 2-(2-methylenecycloalkyl)-furan derivatives by Pd-catalyzed cycloreduction.

[structure: see text]. We have discovered a new method employing Pd-catalyzed cycloreduction of conjugated enynals 1 bearing an alkyne unit leading to the corresponding 2-(2-methylenecycloalkyl)-furans 2a-j and a related compound 7 in good to excellent yields.

Highly efficient [2 + 2] intramolecular cyclizations of allenynes under microwave irradiation: construction of fused bicyclic compounds.

A palladium [2 + 2] cycloaddition of 1,6- and 1,7-allenyne carboxylates and microwave-mediated [2 + 2] cycloaddition of various 1,n-allenynes were developed and, particularly, the microwave irradiated [2 + 2] cycloaddition of allenynes can provide a simple, general and eco-friendly synthetic method to fused bicyclo[m,2,0]alkadienes.

Decarbopalladation of pi-allylpalladium intermediates formed from palladium-catalyzed arylations of 3-allen-1-ols.

[reaction: see text] Unusual palladium-catalyzed arylative fragmentations of acyclic 3-allen-1-ols were observed. Oxidative addition of Pd(0) to aryl halides would form the arylpalladium halides, which added to the central carbon of allenes via carbopalladation to form the pi-allylpalladium intermediates. The pi-allylpalladium intermediates would be reductively eliminated via carbon-carbon cleavage to give the arylated dienes and the alpha-hydroxyalkylpalladium intermediates, which were further reductively eliminated to the corresponding aldehydes.