Visible-Light Photoredox-Catalyzed Direct Decarboxylative Functionalization of α-Keto Acids.

A novel and environmentally friendly photocatalytic strategy is presented for generating acyl radicals from benzoylformic acids, which are subsequently trapped by various sulfone-based SOMOphiles. This strategy provides a robust toolkit to access a variety of synthetically important functionalized aryl-ketone derivatives, which efficiently and directly construct acyl-S, acyl-Se, acyl-C, and acyl-N bonds. The broad substrate scope, excellent functional group compatibility, and mild reaction conditions make this protocol practical and attractive.

Photochemical radical decarboxylative disulfuration of α-keto acids and oxamic acids.

A visible-light-induced directed decarboxylative disulfuration of α-keto acids and oxamic acids was developed. As a result, a series of versatile mono acyl disulfide derivatives was synthesized under mild and sustainable reaction conditions. This protocol has a broad substrate scope, good functional-group tolerance, and excellent synthetic applications.

1,2-Alkynyl Functionalization of Unactivated Alkenes via Diverse Radical-Triggered Functional Group Migration.

We have developed a transition-metal-free radical approach for 1,2-alkynyl functionalization of unactivated alkenes through the combination of 3-exo-dig cyclization with alkynyl migration triggered by in situ-generated diverse radical precursors. This strategy provides a robust toolkit to access a variety of synthetically important α-functionalized alkynyl ketones, simultaneously installing densely functionalized carbonyl, alkynyl, and other various functional groups into the alkenes. The broad substrate scope, which includes distinctly electron-donating or electron-withdrawing alkynyl migrating groups, excellent functional group compatibility, and remarkable selectivity make this protocol practical and attractive.