Sustainable electrochemical dehydrogenative C(sp3)-H mono/di-alkylations

Catalyst-free, direct electrooxidative phenol derivatives C(sp(3))-H mono- and di-alkylation reaction have been developed. In contrast to previous typical oxidative and electrochemical coupling, this electrosynthetic approach enables selective mono- and di-alkylations through metal- and external oxidant-free mild conditions via easily available electrodes. Advances of this strategy were proven by an unparalleled broad substrate scope for efficient C-C, C-N, C-O bond formation as well as excellent site- and regioselectivity. The electrochemical selective alkylations were devoid of additional electrolytes, could be conducted on a gram scale, and provided the enone products by cascade electrooxidative dehydrogenation, which highlight a notable potential for further late-stage diversification. Detailed mechanistic studies allowed to delineate the exact profile of the generation of the mono- and di-alkylation events.

Automated summary

A novel catalyst-free, direct electrooxidative method has been developed for the mono- and di-alkylation of phenol derivatives at C(sp(3))-H. This approach allows for selective alkylations under mild conditions without the need for metals or external oxidants, using readily available electrodes. The study demonstrates a broad substrate scope and excellent selectivity for C-C, C-N, C-O bond formation, with the potential for further late-stage diversification.