Selective aromatic substitution is a long-standing goal in organic chemistry. [1] Recently, a new method involving a palladium-catalyzed process based on a sequential double aromatic substitution and an intermolecular Heck reaction leading to o,o'-disubstituted vinylarenes 2 was described (Scheme 1). [2] The potential of this strategy is truly remarkable since it allows the formation of three new carbon ± carbon bonds in a one-pot process.

A copper-catalyzed direct alkenylation of oxazoles with bromoalkenes has been developed. The method is both regio- and stereoselective and tolerates a variety of functional groups. A wide range of 2-E-vinyl-substituted oxazoles were obtained in high yields including the highly fluorescent alkaloid annuloline.

[reaction: see text] Iodocyclizations are important transformations and among stereocontrolled iodocyclizations mostly substrate-controlled versions using a chiral auxiliary have been successfully investigated. This work reports on stereoselective reagent-controlled iodolactonizations applying a new method using a combination of ICl and a primary amine leading to the highest selectivities known so far.