Science of Synthesis

Rück-Braun, K.; Priewisch, B., Science of Synthesis, (2007) 31, 1355.

Nitrosoarenes are highly reactive substrates and tend to form complexes with many metals.[‌142‌] Furthermore, they undergo a plethora a potentially useful reactions (‌Scheme 53‌). For example, nitrosoarenes are easily oxidized to the corresponding nitroarenes or reduced to give the corresponding amines. The Mills condensation with arylamines is an important method for the formation of diaryldiazenes ‌108‌ (see Section ‌31.25‌). With alkenes containing an allylic hydrogen, nitrosoarenes form allylic N-arylhydroxylamines ‌109‌ in a nitroso–ene reaction.[‌143‌] Further electrocyclic reactions include [2 +2] and [4+2] cycloadditions that yield 2,4,4-triaryloxazetidinones ‌110‌ and 2-aryldihydrooxazines ‌111‌, respectively.[‌144‌,‌145‌] Since dihydrooxazines ‌111‌ can be easily transformed into biologically relevant compounds, the nitroso Diels–Alder reaction has been successfully applied in the synthesis of natural products.[‌146‌] Reacting as carbonyl analogues, nitrosoarenes add organometallic nucleophiles giving N,N-diarylhydroxylamines ‌112‌, which can be easily reduced to the corresponding diarylamines.[‌147‌] Base-catalyzed condensation with compounds containing active methylene groups (the Ehrlich–Sachs reaction) furnishes N-arylimines ‌113‌ or nitrones ‌114‌.[‌148‌,‌149‌] Several nitrosoarenes are used as spin traps ‌115‌ for the investigation of short-lived radical processes.[‌150‌] The organo-catalyzed nitrosoaldol reaction is an attractive method for the enantioselective α-amination and α-oxygenation of carbonyl compounds and yields derivatives of the type ‌116‌ or ‌117‌. This chemistry is currently the focus of intensive investigation.[‌145‌,‌151‌,‌152‌]

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References

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• 8.Meeeee-Meee, (8888) 88/8, 8888.
• 8.Meeeee-Meee, (8888) M 88e8, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 888.