1.
Fluorine as a Traceless Directing Group for the Regiodivergent Synthesis of Indoles and Tryptophans.
J Am Chem Soc
; 140(40): 13034-13041, 2018 10 10.
Article
in English
| MEDLINE
| ID: mdl-30183276
ABSTRACT
Despite ample evidence for the unique reactivity offered by hypervalent F-iodanes, mechanistic investigations fall far behind. In order to shed light on the unusual behavior of such F-reagents, we conducted computational and experimental studies on the chemodivergent transformation of styrenes. We identified the spirocyclic F-cyclopropane as the common intermediate for both the C, H-fluorination and C, H-amination pathways. The fate of this key compound is determined by the extent of cationic charge delocalization controlled by the N-substituents. Exploiting this phenomenon, a multitude of different transformations have become available, leading, i.e., to the regiodivergent synthesis of indoles and tryptophans.