A Synthetic Cycle for Heteroarene Synthesis by Nitride Insertion

• Published in: Angewandte Chemie International Edition Vol. 61; no. 46; pp. e202213041 - n/a
• Main Authors: Kelly, Patrick Q., Filatov, Alexander S., Levin, Mark D.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 14.11.2022; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Chemical synthesis; Communication; Communications; Computer applications; Crystallography; Heterocycles; Insertion; Inserts; Intermediates; Metal nitrides; Nitrogen; Osmium; Reaction Mechanisms; Reagents; Skeletal Editing; Transition Metal Nitrides; Transition metals; Heterocycles; Transition Metal Nitrides; Skeletal Editing; Osmium; Reaction Mechanisms
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202213041

Recent interest in skeletal editing necessitates the continued development of reagent classes with the ability to transfer single atoms. Terminal transition metal nitrides hold immense promise for single‐atom transfer, though their use in organic synthesis has so far been limited. Here we demonstrate a synthetic cycle with associated detailed mechanistic studies that primes the development of terminal transition metal nitrides as valuable single‐atom transfer reagents. Specifically, we show [cis‐terpyOsNCl2]PF6 inserts nitrogen into indenes to afford isoquinolines. Mechanistic studies for each step (insertion, aromatization, product release, and nitride regeneration) are reported, including crystallographic characterization of diverted intermediates, kinetics, and computational studies. The mechanistic foundation set by this synthetic cycle opens the door to the further development of nitrogen insertion heteroarene syntheses promoted by late transition metal nitrides. An osmium nitride is shown to insert nitrogen into indenes to afford isoquinolines. A synthetic cycle to regenerate the starting nitride is presented alongside mechanistic studies of each step.