The Nitroso Ene Reaction:  A Regioselective and Stereoselective Allylic Nitrogen Functionalization of Mechanistic Delight and Synthetic Potential

Shape‐Switchable Azo‐Macrocycles

“…This is also the reason why the Mills reaction is better for an asymmetric target compound. The nitroso precursor [187]- [189] for the Mills reaction can either by synthesized by a selective reduction (pathway g) from the nitro compound or by a selective oxidation starting from an amine. In contrast to this one step synthesis, the precursor for the palladium catalyzed hydrazines coupling needs a three step reaction.…”

A new life for nitrosocarbonyls in pericyclic reactions

“…2 Due to the high reactivity of nitrosocarbonyls, they are usually generated in situ through the oxidation of hydroxamic acids. Since their discovery by Kirby However most of the cited methods have certain limitions.…”

“…9 Further, strong oxidative conditions limit the use of functional groups and can reduce the stability of the formed adducts. 2 Moreover, an excess of olefin is required in ER in order to obtain high yields of ene product. 10,11 In the last two years attention has been paid to developing new generation methods compatible with a wider plethora of functional groups, and more environmentally friendly.…”

“…The 3,6-dihydro-1,2-oxazines, obtained through reaction of nitrosocarbonyls with different dienes, allow for the rapid construction of a wide variety of molecular scaffolds that have been used in the synthesis of natural products, azasugars, amino acid derivatives and carbocyclic analogues. 2 The acylnitroso ene reaction constitutes a mild and valuable synthetic methodology to obtain allylamine through the direct allylic amination of olefins. Allylamines are versatile and fundamental building blocks for the construction of α-and β-amino acids, alkaloids and carbohydrate derivatives.…”

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].…”