Rich chemistry of nitroso compounds

Abstract

Nitrosobenzene or nitrosopyridine are found to be attractive electrophiles in catalytic enantioselective carbon-nitrogen and/or carbon-oxygen bond forming reactions. In the presence of designer Lewis or Brønsted acid catalysts, catalytic enantioselective O- and N-nitroso aldol reaction or nitroso Diels-Alder reaction proceed smoothly. The scope and limitation of new catalytic processes are described.

Reactivity of 4-Nitrosoanilines Towards Dimeric Halogenido-bridged Complexes of Iridium(III) and Rhodium(III) of the Type [(η5- C5Me5)MX2]2

“…Not only due to its rich coordination chemistry with eleven different main coordination modes to metal centers [8,9], the family of C-nitroso compounds has been investigated extensively. Also the possible applications in organic synthesis [10], for example the nitroso ene [11] or nitroso Diels-Alder reaction [12 -14] attracted attention. The most important properties of the NO function for these applications are the high reactivity based upon the polarization of the N-O bond and the specific structure in the equilibrium between nitroso monomer and azodioxy dimer which leads to a unique chemo-and regioselectivity [10].…”

“…Also the possible applications in organic synthesis [10], for example the nitroso ene [11] or nitroso Diels-Alder reaction [12 -14] attracted attention. The most important properties of the NO function for these applications are the high reactivity based upon the polarization of the N-O bond and the specific structure in the equilibrium between nitroso monomer and azodioxy dimer which leads to a unique chemo-and regioselectivity [10]. Since the discovery of the important roles of C-nitroso derivatives in various biological processes [15 -23], their significance is also affirmed in biochemistry.…”

Nitrosobenzene

“…In the presence of Lewis or Brønsted acid catalysts, enantioselective nitroso aldol or nitroso Diels-Alder reactions proceed under smooth conditions. 1 Nitrosobenzene can be used in the aminoxylation of aldehydes and ketones, and the products are precursors of 1,2-amino alcohols, terminal diols 2 and allylic alcohols. 3 It can also be used in asymmetric desymmetrization of a-hydroxy ketones.…”

Highly Regio‐ and Enantioselective Nitroso Diels−Alder Reaction of 1,3‐Diene‐1‐carbamates Catalyzed by Chiral N,N′‐Dioxide/Copper(II) Complex

“…The chemistry of nitroso compounds has attracted much attention in recent years, [1] especially because of its convenient construction of molecules containing both nitrogen and oxygen atoms. The nitroso DielsÀAlder reaction, [2] nitroso aldol reaction [3] and nitroso ene reaction, [4] have achieved significant progress.…”