Hantzsch Ester-Mediated Photochemical Transformations in the Ketone Series: Remote C(sp(3))-H Arylation and Cyclopentene Synthesis through Strain Release

摘要

A metal-free Hantzsch ester-mediated synthesis of cyclopentenylketones as well as gamma-hetarylketones starting from ketocyclopropanes under eco-friendly conditions was developed. The versatility of the developed conditions is shown by reacting ketocyclopropanes in both a formal [3 + 2] cycloaddition with terminal alkynes (further investigated using theoretical calculations) and a radical C-C-coupling with cyanopyridines. The newly developed methodologies were later on utilized as a downstream reaction for photogenerated cyclopropanes combining UV and visible light photochemistry. Following this procedure, a UV-driven Norrish-Yang-type reaction induces the ring strain of the intermediates, which serves as activation energy for the subsequent ring transformation.