Nitrene transfer from a sterically confined copper nitrenoid dipyrrin complex.

ABSTRACT: Despite the myriad Cu-catalyzed nitrene transfer methodologies to form new C-N bonds (e.g., amination, aziridination), the critical reaction intermediates have largely eluded direct characterization due to their inherent reactivity. Herein, we report the synthesis of dipyrrin-supported Cu nitrenoid adducts, investigate their spectroscopic features, and probe their nitrene transfer chemistry through detailed mechanistic analyses. Treatment of the dipyrrin Cu^I complexes with substituted organoazides affords terminally ligated organoazide adducts with minimal activation of the azide unit as evidenced by vibrational spectroscopy and single crystal X-ray diffraction. The Cu nitrenoid, with an electronic structure most consistent with a triplet nitrene adduct of Cu^I,

SUBMITTER: Carsch KM 

PROVIDER: S-EPMC10566472 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature