General Access to Clavine Alkaloids via a Rhodium(I)‐Catalyzed Diastereoselective Hayashi‐Miyaura Reaction

Abstract We report the development of the diastereoselective rhodium(I)‐catalyzed intramolecular conjugate addition (Hayashi‐Miyaura reaction) of robust and easily handled 4‐pinacolboronic ester D‐tryptophan derivatives tethering an activated alkene as the acceptor. This methodology provides, access to the functionalized chiral tricyclic core of the ergoline skeleton diastereoselectivity and allows further modification for the cyclization of the fused fourth ring present in several clavine alkaloids.