Here is an interesting piece of work by Narbonne, Retailleau, Maestri and Malacria from the CNRS and the University of Paris detailing the synthesis of dibenzoazepines via a three component reaction catalysed by palladium/norbornene complexes.
Using the following conditions: Pd(OAc)2 5 mol %, 0.02 M, ligand 10 mol %, norbornene 60 mol %, Ar−I 0.29 mmol, 1.1 equiv, olefin 2 equiv, K2CO3, 2.2 equiv in DMF under Ar at 130 °C for 36 h. When the ligand is a tri-isopropylphosphine the yields are around 75%, unfortunately determined by H-NMR!
The paper goes into great mechanistic detail to account for the observed diastereoselectivity. Interestingly when the olefin is methyl vinyl ketone, an enolisable ketone, a retro-Mannich reaction occurs delivering the second of the two products shown above. The selectivity is due to a chelated Pd(IV) complex that allows atroposelective aryl-aryl coupling, simultaneously a kinetic resolution of the intermediates takes place resulting in the observed selectivity.
This is a nice method to rapidly access biologically interesting dibenzo[c,e]azepines as well as generating novel organocatalysts. However, I would like to see a scale-up of this sequence and a better determination of the yield. NMR yields can be taken with a pinch of salt. Otherwise some interesting chemistry here.