C3 Functionalization of Indolizines via HFIP-Promoted Friedel–Crafts Reactions with (Hetero)arylglyoxals

[Image: see text] A highly efficient Friedel–Crafts type hydroxyalkylation at the C3 position of indolizines with (hetero)arylglyoxals has been achieved by the action of hexafluoroisopropanol (HFIP) under mild reaction conditions, leading to direct access to a variety of polyfunctionalized indolizines in excellent yields. Installation of more diverse functional groups at the C3 site of indolizine scaffold was realized via further elaboration of the resulting α-hydroxyketone moiety, allowing for expansion of indolizine chemical space.