Nitrosyl Triflate and Nitrous Anhydride, Same Mode of Generation, but Very Different Reaction Pathways. Direct Synthesis of 1,2-Oxazetes, Nitroso or Bisoxazo Compounds from Olefins.

Abstract

Nitrosyl triflate (TfONO) can be generated in situ from tetra-n-butylammonium nitrite and triflic anhydride (1:1) in CH2Cl2 solution at ca. -30 °C. It acts as a powerful and soluble nitrosating agent with a wide range of olefinic or aromatic substrates. Nitrous anhydride (O═N-O-N═O) can be generated in the same way using tetra-n-butylammonium nitrite and triflic anhydride (2:1) in CH2Cl2 solution at ca. -30 °C. Each reagent has been isolated and characterized. They react with olefins to give different products. Nitrosyl triflate is an excellent reagent for generating either vinylic or allylic nitroso compounds or their dimeric bisoxazo derivates. Nitrous anhydride efficiently converts many olefins to 1,2-oxazetes in a single step, making this class of compounds readily available from olefins for the first time. We have also discovered another route to 1,2-oxazetes involving a novel rearrangement/isomerization of allylic nitroso compounds which is catalyzed by Pd-C/H2.