Nitration of .alpha.-olefins in noncomplexing solvents and novel reactions of the products

Bonetti, G.; DeSavigny, Chester B.; Michalski, Conrad; Rosenthal, Rudolph

doi:10.1021/jo01265a047

Cited by 17 publications

(4 citation statements)

References 1 publication

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“…67 These studies have largely confirmed Schechter’s original proposal of a radical mechanism, 68 in which NO 2 undergoes addition to the less substituted alkene position to form a β-nitroalkyl radical 37 . Trapping of this intermediate with a second molecule of NO 2 then forms both dinitro 32 and nitro-nitronite 37 addition products.…”

Section: Binary Nitrogen Oxides and Related Reagentsmentioning

confidence: 61%

Methods for direct alkene diamination, new & old

2012

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The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise.

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Section: Binary Nitrogen Oxides and Related Reagentsmentioning

confidence: 61%

Methods for direct alkene diamination, new & old

2012

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“…Based on the literature (35,(43)(44)(45)(46)(47)(48)(49)(50)(51)(52)(53), this can occur by either a C-N or a C-O attachment to give the dinitro or the nitronitrite {Scheme 2). Nitronitrites are unstable, and undergo elimination of nitrous acid to give the vinyl nitro compound (45,46), hydrolyze to the nitro alcohol in the presence of water or alcohol (43)(44)(45)(46)(47)(48)(49)(50)(51)(52)(53), or oxidize to the nitronitrate in the presence of excess oxygen {48-55). The results of this product study of POPC with NO2/N204 are therefore consistent with earlier studies with alkenes.…”

Section: Discussionmentioning

confidence: 99%

Reactions of dinitrogen pentoxide and nitrogen dioxide with 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine

Lai

Finlayson-Pitts

1991

Lipids

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The reactions of gaseous dinitrogen pentoxide (N2O5) and nitrogen dioxide (NO2) with 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphocholine (POPC) coated on the inside surface of a glass reaction cell were studied at 298 K. Unsaturated phosphatidylcholines are significant components of pulmonary surfactant in the alveolar region of the lung and hence serve as a simple model to examine reactions of pulmonary surfactant with these oxidant air pollutants. Using high-performance liquid chromatography (HPLC), Fourier transform infrared and fast atom bombardment mass spectroscopy, the major products of reactions of POPC with N2O5 and NO2 were separated and identified. In the POPC-N2O5 reaction using either air or helium as a buffer gas, the nitronitrate, vinyl nitro and allylic nitro derivatives, as well as a small amount of the trans-isomer of the starting material, were obtained. The nature of the products obtained from the POPC-NO2 reaction depends on the concentration of NO2 as well as whether air is present. At low NO2 concentrations (PNO2/N2O4 less than or equal to 3.8 Torr) in air or in helium, the trans-isomer of POPC was formed almost exclusively. At higher NO2 concentrations (PNO2/N2O4 greater than or equal to 20 Torr) in helium, the dinitro, vinyl nitro and nitro alcohol derivatives were formed. In the presence of air (or 24% 18O2 in helium), a nitronitrate and a dinitronitrate were additional products. Mechanisms for the formation of the observed products and implications for the inhalation of oxides of nitrogen are discussed.

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“…Direct incorporation of this methyl group at the Michael addition step, by using methyl β-nitromethacrylate, was thwarted by isomerization of this material under the basic reaction conditions to methyl α-(nitromethyl)acrylate, with ensuing addition-elimination to give i .…”

Section: Referencesmentioning

confidence: 99%

A Template for Stabilization of a Peptide α-Helix: Synthesis and Evaluation of Conformational Effects by Circular Dichroism and NMR

et al. 1997

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The bicyclic diacid 1 was designed as a semi-rigid template for the hydrogen-bonding pattern of a peptide R-helix. The protected precursor 7 was synthesized in eight steps from tert-butyl 3,5-dimethoxybenzoate and linked to L-alanine and L-lactic acid to provide derivatives appropriate for coupling to a peptide. Both the amide 8-N and the ester 12-O were obtained in each of the four diastereomeric forms. The structure of R,R-8-N was determined by X-ray crystallography, which facilitated assignment of the diastereomers and confirmed the intended conformational effects of the quaternary methyl groups. The bicyclic amide and ester derivatives were appended to the peptide EALAKA-NH 2 , and their influence on the conformation was evaluated in aqueous solution using circular dichroism and NMR. The amide analogs have only a slight effect on the appended peptide, whereas the ester-linked template in S,S-9-O induces 32-50% helical character at 23°C and 49-77% at 0°C, depending on the method of determination; significant helical character persists even at 70°C. The ability of the template 1 to induce the helical conformation is related to its structural and electronic complementarity to the N-terminus of the peptide; templating ability disappears when the carboxylate in S,S-9-O is protonated, and it is not observed in the dimethylamide S,S-9-N-a. The structural and dynamical properties of conjugate S,S-9-O were studied by NMR and compared with those of the acetylated heptapeptide 13. The dispersion and temperature dependence of amide hydrogen chemical shifts and the pattern observed for intra-and inter-residue nuclear Overhauser enhancements are all consistent with a significant population of helical conformers within the conformational ensemble of conjugate S,S-9-O, in contrast to the unstructured peptide 13. The generalized order parameter S 2 was derived for each residue from the 15 N T 1 and T 2 relaxation rate constants and 1 H-15 N heteronuclear NOEs determined for the 15 N-labeled derivative of S,S-9-O; these parameters demonstrate a high degree of conformational rigidity along the peptide chain at 4°C, with relative motion increasing for the C-terminal residues. These data are consistent with the chiroptical studies and demonstrate that the template is exceptionally effective in inducing helical behavior in an appended peptide.

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Nitration of .alpha.-olefins in noncomplexing solvents and novel reactions of the products

Cited by 17 publications

References 1 publication

Methods for direct alkene diamination, new & old

Methods for direct alkene diamination, new & old

Reactions of dinitrogen pentoxide and nitrogen dioxide with 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine

A Template for Stabilization of a Peptide α-Helix: Synthesis and Evaluation of Conformational Effects by Circular Dichroism and NMR

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