Helicity-modulated remote C-H functionalization.

Abstract

Remote C-H functionalization is highly important for the conversion and utilization of arenes, but the conventional routes are comprehensively developed with the assistance of transition metal catalysts or templates. We report a facile metal/template-free electrochemical strategy for remote C-H functionalization in a helical system, where aromatic or aliphatic hydrogen act as a directing group to promote the alkoxylation at the opposite site of the helical skeleton by generating a unique helical "back-biting" environment. Such helicity-modulated C-H functionalization is prevalent for carbo[<i>n</i>]helicenes (<i>n</i> = 6 to 9, primitive or substituted) and hetero[6]helicenes and also occurs when the aryl hydrogen on the first position is replaced by a methyl group or a phenyl group. Thus, the relatively inert helicene skeleton can be precisely furnished with a rich array of alkoxy pendants with tunable functional moieties. Notably, the selective decoration of a methoxy group on <i>N</i>-methylated aza[6]helicene close or distant to the nitrogen atom leads to distinct luminescence variation upon changing the solvents.