Radical-Polar Crossover Catalysis with a d0 Metal Enabled by a Redox-Active Ligand

19 August 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Radical-polar crossover mechanisms are invoked in numerous late transition metal and photocatalyzed reactions. To the best of our knowledge, reductive radical-polar crossover mechanisms are not invoked for group 3 early transition metals due to their propensity to exist in high oxidation states. Through use of a redox-active (tris)amido ligand we have accessed this mechanism for use with early transition metals. This mechanism is showcased through enabling product formation for a wide variety of elimination products from -halo substituted benzylic bromides. The mechanism of this new type of reactivi-ty with Sc is explored and Hammett analysis reveals an anionic intermediate. The wide functional group tolerance of this reaction is also demonstrated.

Keywords

redox-active ligands
radical polar crossover
d0 metals

Supplementary materials

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