Photochemical Carbene Transfer Reactions of Aryl/Aryl Diazoalkanes-Experiment and Theory*.

ABSTRACT: Controlling the reactivity of carbene intermediates is a key parameter in the development of selective carbene transfer reactions and is usually achieved by metal complexes via singlet metal-carbene intermediates. In this combined experimental and computational studies, we show that the reactivity of free diaryl carbenes can be controlled by the electronic properties of the substituents without the need of external additives. The introduction of electron-donating and -withdrawing groups results in a significant perturbation of singlet triplet energy splitting of the diaryl carbene intermediate and of activation energies of consecutive carbene transfer reactions. This strategy now overcomes a long-standing paradigm in the reactivity of diaryl carbenes and allows the realization of highly ch

SUBMITTER: Jana S 

PROVIDER: S-EPMC8252492 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature