%0 Journal Article %A Huang, Xiaoqiang %A Webster, Richard D. %A Harms, Klaus %A Meggers, Eric %D 2016 %T Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer %U https://acs.figshare.com/articles/journal_contribution/Asymmetric_Catalysis_with_Organic_Azides_and_Diazo_Compounds_Initiated_by_Photoinduced_Electron_Transfer/3827571 %R 10.1021/jacs.6b07692.s001 %2 https://ndownloader.figshare.com/files/5972871 %K α- diazo carboxylic esters %K Diazo Compounds Initiated %K aryl azides %K 2- acyl imidazoles %K chiral-at-metal rhodium-based Lewis acid %K substrate %K Photoinduced Electron Transfer Electron-acceptor-substituted aryl azides %K photoredox %X Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction. %I ACS Publications