A DFT study on palladium-catalyzed decarboxylative intramolecular aziridination reaction mechanism

Divergent Catalytic Approach from Cyclic Oxime Esters to Nitrogen-Containing Heterocycles with Group 9 Metal Catalysts

“…It is assumed that the skeletal rearrangement of bicyclic aziridine 2 to azabicyclic cyclopropane 6 would be triggered by the coordination of the nitrogen atom to the Lewis acidic metal species, , taking the control experiments as shown in Table into consideration. Then complex F undergoes a C–N bond-cleaving ring expansion simultaneously with the formation of the C–I bond to form six-membered species G , which readily undergoes the C–C bond-forming recyclization to give bicyclic product 6 , regenerating the metal iodide species (Scheme ).…”

Synthesis of Imidazoles and Pyrimidines Using Palladium-Catalyzed Decar­boxylative Intramolecular Condensation of 1,2,4-Oxadiazol-5(4H)-ones

“…[9][10][11] Decarboxylation from A generates the palladium-iminonitrene complex B. 12 Another possible active intermediate may be the four-membered diazapalladacycle B′. When enough Ph 3 P exists in this system, iminophosphorane C is preferentially formed by fast nitrene transfer from intermediate B or B′ to phosphine and undergoes intramolecular aza-Wittig-type condensation accompanied with isomerization to afford imidazole 4 and triphenylphosphine oxide (path a).…”

Activation of N−O σ Bonds with Transition Metals: A Versatile Platform for Organic Synthesis and C−N Bonds Formation**

“…This step is followed by reductive elimination to regenerate the Pd(0)-catalyst, giving the bicyclic system 44 (Scheme 11b). [54] Careful choice of the metal/ligand system coupled with different substituents on the substrate can vastly influence the outcome of such transformations. In a follow-up study, Ohe et al were able to streamline this idea further and use the same class of substrates to access highly substituted pyridines 48.…”