Three decades of unveiling the complex chemistry of C-nitroso species with computational chemistry

Abstract

This review revisits the complex reactivity of C-nitroso derivatives through the synergistic combination of computational and synthetic organic chemistry, with an emphasis on the rationalization of mechanisms and selectivities.

Enantioselective and Regiodivergent Synthesis of Dihydro-1,2-oxazines from Triene-Carbamates via Chiral Phosphoric Acid-Catalysis

“…To improve our understanding of the mechanism and the regioselectivity observed experimentally, a computational study was performed using compounds 1a , 1g , and 2a . Both uncatalyzed and H + -catalyzed pathways were considered, taking into account the 2,3- s - trans /4,5- s - cis and 2,3- s - cis /4,5- s - trans conformations of the triene-carbamates.…”

Peroxidase-induced C–N bond formation via nitroso ene and Diels–Alder reactions

“…Among the various different ways to conduct carbon-nitrogen bond formations, nitroso reactions occupy something of a niche. [3] Nevertheless, their distinctive reaction profile with a high affinity for ene and diene reaction partners also puts nitroso species in a unique position where they complement more traditional methodologies such as condensations or cross coupling reactions in offering an alternative pre-functionalization strategy. First explored in the 1940's, nitroso-Diels-Alder cycloadditions and nitroso-ene reactions later in the 1960's are nowadays found as key transformations in a large number of total syntheses yielding natural products and pharmaceuticals.…”

Nitroso-Ene-type Cyclization Toward Diversified Synthesis of Amino Deoxysugars: A Proof of Concept

“…Additionally, conformational flexibility of the olefin motif may form different diastereomers with subtle energy differences. Although the detailed mechanisms remain presently unclear at this stage, the benzoylated derivatives 12a – 12c were further subjected to the N–O bond cleavage by SmI 2 with good yields of the corresponding amides (Table ). Finally, treating the bisilylated oxazolinones 12a and 12b with AcCl–MeOH yielded amino deoxysugars 1c and 1d (α/β = 1/1.7) as a protected form of L -daunosamine.…”