The rhodium-catalyzed asymmetric N-selective and regioselective coupling of triazole derivatives with internal alkynes and terminal allenes gives access to secondary and tertiary allylic triazoles in very good enantioselectivities. For this process, three new members of the JosPOphos ligand family have been prepared and employed in catalysis. The optimized reaction conditions enable the coupling of triazoles with internal alkynes as well as with allenes, displaying a high tolerance for functional groups. A gram scale reaction provided N-allyltriazole, which was subjected to various transformations highlighting synthetic utility.

Concise syntheses of the Hancock alkaloids (−)-angustureine and (−)-cuspareine are presented, applying and refining a recently developed rhodium-catalyzed hydroamination for the stereoselective construction of the chiral secondary amine. Furthermore, the syntheses include an allene synthesis via boron–magnesium exchange as well as the construction of the tetrahydroquinoline motive via a hydroboration/Suzuki–Miyaura coupling sequence.

A rhodium-catalyzed regio- and enantioselective cyclization of tethered allenylbenzenes is reported.

A short and efficient total synthesis of the C -symmetric (-)-cylindrocyclophane F is presented, using a cross olefin metathesis dimerization strategy for construction of the [7,7]-paracyclophane macrocycle. The synthesis of the dimerization building block includes a Pd-catalyzed sp -sp Negishi cross coupling of a sterically hindered Zn-reagent with an aromatic triflate, an enantiospecific Zn-catalyzed sp -sp cross coupling of an α-hydroxy ester triflate with a Grignard reagent and the application of an enantioselective Rh-catalyzed C-allylation of an electron rich arene.