Lewis Acid-Promoted Hetero Diels−Alder Cycloaddition of α-Acetoxynitroso Dienophiles

Calvet, Géraldine; Dussaussois, Marion; Blanchard, Nicolas; Kouklovsky, Cyrille

doi:10.1021/ol0491336

Cited by 59 publications

(29 citation statements)

References 33 publications

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“…3, path a) (12). Kinetic studies and 15 N NMR experiments show that initial deprotonation occurs at the nitrogen atom to give the N-anion (structurally similar to monoprotonated Angeli's salt) that undergoes S-N bond heterolysis to yield the products (12). The benzenesulfinate ion, the organic by-product, should act as a good nucleophile and modest reducing agent and these properties should be considered in biological experiments.…”

Section: Structure/synthesismentioning

confidence: 99%

“…While metabolic activation of cyanamide forms the cyanide ion, evidence of cyanide toxicity during cyanamide use has generally not been reported (32). Gas chromatographic analysis of the reaction headspace using both 14 N-and 15 N-labeled cyanamide identifies nitrous oxide as evidence of HNO formation and the nitrogen atoms of cyanamide as the ultimate source of HNO (60). Although N-hydroxycyanamide provides an alternative structural platform for new HNO donors, the possibility of cyanide formation severely limits the development of these compounds as new therapeutics.…”

Section: Mechanism/rate Of Hno Release/by-productsmentioning

confidence: 99%

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The Chemistry of Nitroxyl-Releasing Compounds

DuMond

King

2011

Antioxidants & Redox Signaling

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Nitroxyl (HNO) demonstrates a diverse and unique biological profile compared to nitric oxide, a redox-related compound. Although numerous studies support the use of HNO as a therapeutic agent, the inherent chemical reactivity of HNO requires the use of donor molecules. Two general chemical strategies currently exist for HNO generation from nitrogen-containing molecules: (i) the disproportionation of hydroxylamine derivatives containing good leaving groups attached to the nitrogen atom and (ii) the decomposition of nitroso compounds (X-N=O, where X represents a good leaving group). This review summarizes the synthesis and structure, the HNO-releasing mechanisms, kinetics and by-product formation, and alternative reactions of six major groups of HNO donors: Angeli's salt, Piloty's acid and its derivatives, cyanamide, diazenium diolate-derived compounds, acyl nitroso compounds, and acyloxy nitroso compounds. A large body of work exists defining these six groups of HNO donors and the overall chemistry of each donor requires consideration in light of its ability to produce HNO. The increasing interest in HNO biology and the potential of HNO-based therapeutics presents exciting opportunities to further develop HNO donors as both research tools and potential treatments.

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Section: Structure/synthesismentioning

confidence: 99%

Section: Mechanism/rate Of Hno Release/by-productsmentioning

confidence: 99%

The Chemistry of Nitroxyl-Releasing Compounds

DuMond

King

2011

Antioxidants & Redox Signaling

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“…6–13 Angeli’s salt (Na 2 N 2 O 3 ) and Piloty’s acid (PhSO 2 NHOH, N-hydroxy benzenesulfonamide) represent the most widely used HNO donors but numerous structurally and mechanistically diverse HNO donors have appeared, including acyloxy nitroso compounds. 14–19 While stable acyloxy nitroso compounds react as N-O heterodienophiles, 20 relatively little work describing their synthetic potential has appeared and we report two distinct ring expansions of acyloxy nitroso compounds.…”

Section: Introductionmentioning

confidence: 85%

“…20 Under these conditions, acyloxy nitroso compound ( 2a ) disappears and both ketone ( 4a ) and oxime ( 5a ) form as byproducts. Similar treatment of the acyloxy nitroso compound derived from 2-methyl cyclopentanone ( 2b ) gives the ring expanded cyclic hydroxamic acid ( 3b ) in 77% yield.…”

Section: Expansion To Cyclic Hydroxamic Acidsmentioning

confidence: 99%

Ring expansions of acyloxy nitroso compounds

Hadimani

Mukherjee

Banerjee

et al. 2015

Tetrahedron Letters

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Treatment of cyclopentanone and cyclobutanone-derived oximes with lead (IV) tetraacetate gives the bright blue acyloxy nitroso compounds, which upon basic hydrolysis yields the ring expansion product cyclic hydroxamic acids in 12–81% yield. Reactions of substituted cyclopentanones provide ring expanded products where the –NOH group regioselectively inserts to the more substituted position and gives a better yield compared to the treatment of the same ketone with a basic solution of Piloty’s acid. Reaction of phosphines with acyloxy nitroso compounds generally generates a ring-expanded Beckmann rearrangement product that can be hydrolyzed to the corresponding lactam. Acyloxy nitroso compounds that undergo rapid hydrolysis to HNO do not show this ring expansion reactivity. These results further demonstrate the versatility of acyloxy nitroso compound to yield structurally complex materials.

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“…4 Some years ago, we have described the in situ cleavage of N-O bond during the nitroso Diels-Alder reaction between an acetoxynitroso derivative and various dienes. [5][6][7] This nonreductive bond cleavage was assumed to involve an enamine intermediate which underwent fragmentation to give an hydroxyimine that was further hydrolyzed. This procedure allowed the direct synthesis of 1,4-amino alcohols from dienes.…”

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confidence: 99%

Mild Cleavage of N–O Bond of 3,6-Dihydro-1,2-oxazines by Condensation of Aldehydes in Aqueous Media

Galvani

Lett

Kouklovsky

2015

Synlett

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The nonreductive cleavage of a model 3,6-dihydro-1,2-oxazine by condensation of 2,2-dimethoxyacetaldehyde under aqueous conditions is investigated. Depending on the pH of the solution, the reaction leads either to the N-acylated 1,4-amino alcohol or to the corresponding stable hemiaminal. The formation of the former is believed to proceed through iminium to oxaziridine rearrangement and not through enamine formation, as confirmed by the use of nonenolizable aldehydes. This procedure allows a very mild, nonreductive cleavage of N-O bonds.

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Lewis Acid-Promoted Hetero Diels−Alder Cycloaddition of α-Acetoxynitroso Dienophiles

Cited by 59 publications

References 33 publications

The Chemistry of Nitroxyl-Releasing Compounds

The Chemistry of Nitroxyl-Releasing Compounds

Ring expansions of acyloxy nitroso compounds

Mild Cleavage of N–O Bond of 3,6-Dihydro-1,2-oxazines by Condensation of Aldehydes in Aqueous Media

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