Catalytic 1,3-Proton Transfer in Alkenes Enabled by Fe═NR Bond Cooperativity: A Strategy for pKa-Dictated Regioselective Transposition of C═C Double Bonds

Transition metal catalyzed alkene double bond transposition usually involves metal hydride intermediates. Despite significant advances in the design of catalysts that dictate product selectivity, control over substrate selectivity is less advanced and transition metal catalysts that selectively transpose double bonds in substrates containing multiple 1-alkene functionalities are rare. Herein, we report that the three-coordinate high spin (S = 2) Fe(II) imido complex [Ph2B(tBuIm)2Fe═NDipp][K(18-C-6)THF2] (1-K(18-C-6)) catalyzes 1,3-proton transfer from 1-alkene substrates to afford 2-alkene transposition products. Mechanistic investigations involving kinetics, competition, and isotope labeling studies, supported by experimentally calibrated DFT computations, strongly support an unusual nonhydridic mechanism for alkene transposition that is enabled by the cooperative action of the iron center and basic imido ligand. As dictated by the pKa of the allylic protons, this catalyst enables the regioselective transposition of C═C double bonds in substrates containing multiple 1-alkenes. The high spin (S = 2) state of the complex allows a wide scope of functional groups to be tolerated, including those that are typical catalyst poisons, such as amines, N-heterocycles, and phosphines. These results demonstrate a new strategy for metal-catalyzed alkene transposition with predictable substrate regioselectivity.