Ligand-controlled divergent formation of alkenyl- or allylboronates catalyzed by Pd, and synthetic applications

The use of different ligands allows the preparation of either allyl- or alkenylboronates by Pd-catalyzed borylation of allylic carbonates containing alkyne groups. Unprecedented borylative cyclisation to alkenylboronates takes place with PCy3. The difficult dissociation of NHC ligands allows borylation of carbonates in the presence of alkynes. Oxidation, regioselective Suzuki coupling, as well as Au-catalyzed cycloisomerisation of boronates illustrate the potential synthetic applications of these reactionsThis work was supported by the MICINN (CTQ2010-15927) and the CAM (Project AVANCAT). We thank the UAM for a fellowship to R. L.-D., and the CCC-UAM for computation tim