Photoredox-Catalyzed Generation of Tertiary Anions from Primary Amines via a Radical Polar Crossover
Austin D. Marchese
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorJulia R. Dorsheimer
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorCorresponding Author
Prof. Tomislav Rovis
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorAustin D. Marchese
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorJulia R. Dorsheimer
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorCorresponding Author
Prof. Tomislav Rovis
Department of Chemistry, Columbia University, New York, NY 10027 USA
Search for more papers by this authorGraphical Abstract
A deaminative radical-polar crossover strategy generating carbanions is reported. This so called “aza-Reformatsky” reaction leverages the use of redox-active imines and an iridium photocatalyst to generate a wide array of tertiary benzylic, heteroarylbenzylic and α-ester anions, which can be trapped with different electrophiles.
Abstract
A method for the generation of tertiary carbanions via a deaminative radical-polar crossover is reported using redox active imines from α-tertiary primary amines. A variety of benzylic amines and amino esters can be used in this approach, with the latter engaging in a novel “aza-Reformatsky” reaction. Electronic trends correlate the stability of the resulting carbanion with reaction efficiency. The anions can be trapped with different electrophiles including aldehydes, ketones, imines, Michael acceptors, and H2O/D2O. Selective anion formation can be achieved in the presence of another equivalent or more acidic C−H bond in both an inter- and intramolecular fashion. Mechanistic studies suggest the intermediacy of a discrete carbanion intermediate.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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