The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes |
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Authors: | Ilana B. Stone Dr. Janis Jermaks Dr. Samantha N. MacMillan Prof. Tristan H. Lambert |
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Affiliation: | 1. Department of Chemistry, Columbia University, New York, NY, USA;2. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA |
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Abstract: | An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis. |
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Keywords: | benzo[c]cinnoline diazenes Kornblum oxidation organocatalysis oxidation |
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