Abstract
This review focuses upon the use of nitroso Diels–Alder reactions as a structural complexity generating reaction that has been so far a quite scarcely treated topic, despite its potential. In particular, the use of N-acyl-1,2-dihydropyridines as a non-symmetrical diene component in nitroso Diels–Alder reactions encompasses an initial diversification of pathways giving rise to different cycloadducts (direct and inverse). Selective elaborations of these cycloadducts, basically using a reagent-based approach, deliver a discrete number of structurally diverse compounds, including some original heterobicyclic scaffolds and functionalized heterocycles. This forward synthetic planning allowed the individuation of a new biologically active compound based on a novel oxadiaza-bicyclic-[3.3.1]-nonene scaffold which is still under preclinical evaluation.
Highlights
Organic reactions that result in the formation of multiple covalent bonds in a regio- and stereoselective fashion are very powerful tools in synthetic organic chemistry
Nitroso Diels–Alder (NDA) reactions belong in their own right to this kind of organic transformations, as they are able to install simultaneously a C−O and a C−N bond in a predictable regio- and stereoselective way [1,2,3,4]
This catalytic asymmetric arylation of pyridine devised by Doyle can be considered as a reliable entry to non-racemic 1,2-dihydropyridines used as starting material at the couple stage
Summary
Organic reactions that result in the formation of multiple covalent bonds in a regio- and stereoselective fashion are very powerful tools in synthetic organic chemistry. The only explicit DOS approach making use of NDA chemistry has been reported by Miller and co-workers some years ago [20]. They prepared several highly functionalized hydroxylamine-containing compounds using Lewis acid-mediated nucleophilic ring-opening reactions of NDA cycloadducts, such as 1a with alcohols. The resulting NDA cycloadducts are in principle valuable compounds that can be elaborated towards the preparation of substituted partially hydrogenated pyridines Notwithstanding this encouraging premise, there are only a couple of papers describing the fundamental aspects of this chemistry using acylnitroso dienophiles that date back to the 1980s [24,25].
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