Radical Chlorodifluoromethylation: Providing a Motif for (Hetero)arene Diversification

A method for the radical chlorodifluoromethylation of (hetero)­arenes using chlorodifluoroacetic anhydride is reported. This operationally simple protocol proceeds under mild photochemical conditions with high functional group compatibility and complements the large body of literature for the trifluoromethylation of (hetero)­arenes. Introduction of the chlorodifluoromethyl motif enables rapid diversification to a wide array of aromatic scaffolds. This work showcases the chlorodifluoromethyl group as an attractive entryway to otherwise synthetically challenging electron-rich difluoromethyl­(hetero)­arenes. Furthermore, facile conversion of the CF₂Cl moiety into the corresponding aryl esters, <i>gem</i>-difluoroenones, and β-keto-esters is demonstrated

Microwave-Assisted Synthesis of Heteroleptic Ir(III)⁺ Polypyridyl Complexes

We report a rapid, one-pot, operationally simple, and scalable preparation of valuable cationic heteroleptic iridium­(III) polypyridyl photosensitizers. This method takes advantage of two consecutive microwave irradiation steps in the same reactor vial, avoiding the need for additional reaction purifications. A number of known heteroleptic iridium­(III) complexes are prepared in up to 96% yield. Notably, this method is demonstrated to provide the synthetically versatile photosensitizer [Ir­(ppy)₂(dtbbpy)]­PF₆ in >1 g quantities in less than 5 h of bench time. We envision this method will help accelerate future developments in visible-light-dependent chemistry