Mechanism Of Ti-Catalyzed Oxidative Nitrene Transfer In [2+2+1] Pyrrole Synthesis From Alkynes And Azobenzene
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY(2019)
Abstract
A combined computational and experimental study on the mechanism of Ti-catalyzed formal [2 + 2 + 1] pyrrole synthesis from alkynes and aryl diazenes is reported. This reaction proceeds through a formally Ti-II/Ti-IV redox catalytic cycle as determined by natural bond orbital (NBO) and intrinsic bond orbital (IBO) analysis. Kinetic analysis of the reaction of internal alkynes with azobenzene reveals a complex equilibrium involving Ti=NPh monomer/dimer equilibrium and Ti=NPh + alkyne [2 + 2] cycloaddition equilibrium along with azobenzene and pyridine inhibition equilibria prior to rate-determining second alkyne insertion. Computations support this kinetic analysis, provide insights into the structure of the active species in catalysis and the roles of solvent, and provide a new mechanism for regeneration of the Ti imido catalyst via disproportionation. Reductive elimination from a 6-membered azatitanacyclohexadiene species to generate pyrrole-bound Ti-II is surprisingly facile and occurs through a unique electrocyclic reductive elimination pathway similar to a Nazarov cyclization. The resulting Ti-II species are stabilized through backbonding into the pi* of the pyrrole framework, although solvent effects also significantly stabilize free Ti-II species that are required for pyrrole loss and catalytic turnover. Further computational and kinetic analysis reveals that in complex reactions with unysmmetric alkynes the resulting pyrrole regioselectivity is driven primarily by steric effects for terminal alkynes and inductive effects for internal alkynes.
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Key words
pyrrole synthesis,azobenzene,alkynes,ti-catalyzed
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