Merging Photoexcited Nitroarenes with Lewis Acid Catalysis for the Anti-Markovnikov Oxidation of Alkenes
Joshua Paolillo, Mahmoud R. Saleh, Ethan Junk, Marvin Parasram
Abstract
Herein we describe the oxidation of alkenes to carbonyls and acetonides via the interplay of photoexcited nitroarenes and Lewis acid catalysis. A wide range of alkenes were oxidized to aldehyde and ketone products with anti-Markovnikov selectivity and to acetonides when acetone was employed as a co-solvent. Mechanistic studies support that Lewis acid coordination to the 1,3,2-dioxazolidine intermediate results in a 1,2-shift to generate carbonyl derivatives and a nucleophilic substitution pathway for the formation of acetonides.
Topics & Concepts
Markovnikov's ruleChemistryCatalysisLewis acids and basesCombinatorial chemistryOrganic chemistryRegioselectivityOxidative Organic Chemistry ReactionsCatalytic C–H Functionalization MethodsSynthesis and Catalytic Reactions