Insertion of sulfonylnitrenes into the carbon-hydrogen bonds of saturated hydrocarbons. Acid-catalyzed thermolysis of N-alkyl sulfonamides

Intermolecular Ritter-Type C–H Amination of Unactivated sp3 Carbons

“…Free nitrenes had been mostly generated in situ by thermolysis or photolysis of azides and those rather harsh conditions often resulted in both low selectivities and safety concerns. 7 Thus, metallonitrenes, also prepared in situ from azides 8 , haloamines, 9 N -arenesulfonyloxycarbamates 10 or iminoiodanes 11 constitute the method of choice for intramolecular C sp3 –H amination. However, due to the instability of metallonitrene intermediates, early intermolecular versions of these reactions generally have not led to high yields and have mostly allowed for the functionalization of benzylic or allylic positions.…”

Metal‐Free Conversion of Methane and Cycloalkanes to Amines and Amides by Employing a Borylnitrene

“…[29] The good yields of up to 85 % (Table 1) are remarkable in view of the lower reactivity of most other free nitrenes in intermolecular CÀH bond-insertion reactions. [11][12][13] Phosphoryl nitrenes show reactivity similar to that of borylnitrene 1 b. [14] The aminoboranes of type 2 b can conveniently be transformed into primary amines RNH 2 4 by alcoholysis or into amides RNHCOAc 5 by acylation (Scheme 3).…”

New approaches for the synthesis of hindered C60‐containing polyphosphazenes via functionalized intermediates

“…This method for synthesizing polyphosphazenes with azide groups also is new, and polyphosphazene 8 is a new reactive polyphosphazene intermediate. It is expected that this new reactive intermediate could be used to prepare many other functional polyphosphazenes because organic azides are important synthetic reagents,27–29 and azide groups possess special reactivity 30–32. Further studies are ongoing research in our laboratory.…”