Org. Chem. Front. [SOPhy]

Abstract:

A totally controlled regiodivergent azidation of activated N-allenamides is presented. Using TMSN3/TBAF, β-azidation of N-allenamides occurs exclusively, yielding vinyl azides. Conversely, employing a TFA/TMSN3 mixture results solely in the formation of γ-azides. A subsequent formal Winstein rearrangement of the latter with DBU produces α-amido vinyl azides. Additionally, δ-difluorinated azides featuring an ynamide are selectively synthesized from ene-ynamides. The practical applicability of these transformations is demonstrated through the formation of cyanide derivatives, trifluoromethyl ketones and primary enamines.

 

 

Reference :

Regio-and Stereoselective Azidation of Activated N-allenamides: an entry to α, β, γ and δ-amido-azides

Dorian Schutz, Maxime Hourtoule and Laurence Miesch

Org. Chem. Front. 2024 - DOI:  https://doi.org/10.1039/D4QO01802H

 

Contact:

Laurence Miesch, team SOPhy, Institut de Chimie de Strasbourg (UMR 7177).