Nitroalkane synthesis. A convenient method for aldehyde reductive nitromethylation

Wollenberg, Robert H.; Miller, S.J.

doi:10.1016/s0040-4039(01)85598-2

Cited by 61 publications

(30 citation statements)

References 16 publications

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“…A single crystal X-ray structure determination (22) proved that this adduct (24) had the threo stereochemistry with respect to the new carbon-carbon single bond, as predicted by the topological rule, and that addition of the nitro-olefin had occurred from the side of the enolate opposite to the isopropenyl group, as expected on steric grounds. The minor adduct (25) was separated from the mother liquor with difficulty by thick-layer chromatography in 7% yield.…”

Section: Resultsmentioning

confidence: 65%

“…The solvent was distilled through a Vigreux column, and the residual concentrate was subjected to preparative gas chromatographyg (140°C for 45 min; heat to 230°C at 40°C min-I; 230°C) to give the following three products (yields determined by analytical gas chr~matography'~ at 210°C using n-hexadecane as internal standard): (a) tricycle-octanone 11; 58%; colorless oil; gas chromatography9 t, = '1-Nitropropene was prepared in 36% overall yield from acetaldehyde and nitromethane using an improved procedure for the nitroaldol condensation (Henry reaction) (24). The dehydration of the nitro-alcohol (without purification of this intermediate) was carried out according to a long-standing recipe (35), which has since been optimized (36).…”

Section: Generalmentioning

confidence: 99%

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Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones

Cory¹,

Anderson²,

Bailey³

et al. 1985

Can. J. Chem.

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. Can. J. Chem. 63, 2618Chem. 63, (1985. Nitro-olefins bicycloannulate the a'-enolates of a-cyclohexenones and a-cyclopentenones by initial addition at -7S°C, followed by further reaction in situ in the presence of hexamethylphosphoramide in refluxing tetrahydrofuran to give tricyclor3.2.1 .0Z,7]octan-6-ones and tricyclo[2.2.1 .02.6]heptan-3-ones in a single synthetic step. The reactions with I-nitropropene and with a nitro-olefin having a more complex P-substituent are stereoselective, forming predominantly the tricyclic diastereomer in which the group derived from the P-substituent of the nitro-olefin is syn to the carbonyl bridge. Based on the isolation of intermediates and side products, the mechanism of the bicycloannulation is shown to proceed via sequential kinetically controlled conjugate addition of the enolate to the nitro-olefin at low temperatures, thermodynamically controlled intramolecular Michael addition at higher temperatures to give a bicyclo[2.2.2]octanone intermediate, and hexamethylphosphoramideassisted expulsion of the nitro group as nitrite ion with formation of the cyclopropane ring. For the first time this type of bicycloannulation has been applied to cyclopentenones, and a one-step synthesis of tricyclenone has been carried out to demonstrate the synthetic utility of this new reaction. [Traduit par le journal] Introduction The development of new methodology for the efficient construction of polycyclic systems has long been a major emphasis of research in organic synthesis. Our own contributions to this work have focussed on the discovery of new bicycloannulation reactions, in which tricyclic structures are formed in a single synthetic operation from monocyclic precursors.' In particular, we have reported a series of methods for the bicycloannulation of cyclohexenes (1 b, 2) and cyclohexenones (la, 3) to give tricyclo[3.2.1 .02.7]octanes (1). This tricyclic system is a salient

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Section: Resultsmentioning

confidence: 65%

Section: Generalmentioning

confidence: 99%

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones

Cory¹,

Anderson²,

Bailey³

et al. 1985

Can. J. Chem.

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“…Removal of these impurities from long chain (> 12 carbons) 2-nitroalkanes proved exceedingly difficult. Described in Sequence 3 is the successful extension of a recently developed primary nitroalkane procedure (16) to the synthesis of long chain secondary nitroalkanes.…”

Section: Synthetic Methodologymentioning

confidence: 99%

Synthesis and spin trapping kinetics of new alkyl substituted cyclic nitrones

Haire¹,

Janzen²

1982

Can. J. Chem.

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Three new nitrones, 5-n-propyl-5-methyl-1-pyrroline-N-oxide (PMPO), 5-n-hexyl-5-methyl-1-pyrroline-N-oxide (HMPO), and 5-n-decyl-5-methyl-1-pyrroline-N-oxide (DeMPO), amphiphilic versions of the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), have been synthesized. A comparative study of the absolute rate constants for formation and decay of the tert-butoxyl spin adducts to these cyclic nitrones as well as 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO) has been undertaken using esr kinetic techniques.

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“…11 Acetylation of 10 followed by reduction with a 1 M solution of sodium borohydride in ethanol affords nitroalkane (11). 11,12 Condensation of aldehyde (9) and nitroalkane (11) furnishes nitro alcohol (12) as a mixture of diastereomers in 66% yield. 11 Acetylation followed by dehydroacetylation of nitro (12) gives 13 as a single regioisomer (δ 7.06 ppm for the nitroalkene proton).…”

mentioning

confidence: 99%

“…11,12 Condensation of aldehyde (9) and nitroalkane (11) furnishes nitro alcohol (12) as a mixture of diastereomers in 66% yield. 11 Acetylation followed by dehydroacetylation of nitro alcohol (12) gives 13 as a single regioisomer (δ 7.06 ppm for the nitroalkene proton). 11 Hydrolysis of ester 13 in refluxing 6 N aq.…”

mentioning

confidence: 99%

Regio- and Stereospecific Syntheses and Nitric Oxide Donor Properties of (E)-9- and (E)-10-Nitrooctadec-9-enoic Acids

2006

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Nitrated fatty acids act as endogenous peroxisome proliferator-activated receptor γ (PPARγ) ligands and nitric oxide (NO) donors. We describe the first specific preparation of the two regioisomers of nitrooleic acid, (E)-9-nitrooctadec-9-enoic acid (1) and (E)-10-nitrooctadec-9-enoic acid (2) from cis-cyclooctene and mono-methyl azelate, respectively. These syntheses rely upon a Henry condensation between a nine-carbon nitro component and a nine-carbon aldehyde. Preliminary chemiluminescence NO detection studies reveal the ability of these nitrated fatty acids to release NO.Nitrated fatty acids have emerged as a unique class of endogenously produced signaling molecules. Initial studies reveal that nitrated derivatives of linoleic acid (18:2) occur in concentrations of ~500 nM in human red blood cells and plasma making nitrated fatty acids the single largest pool of bioactive nitrogen oxides in the vasculature. 1 Additional studies show that nitrolinoleate (LNO 2 ) acts as a ligand of the peroxisome proliferator-activated receptor γ (PPARγ). 2 Activation of this transcription factor results in gene expression that affects numerous critical cellular processes including growth and differentiation, inflammation, metabolic homeostasis and vasomotor processes. 3 Other studies show that LNO 2 also spontaneously releases nitric oxide (NO), an endogenous free radical signaling mediator that regulates a number of biological processes including blood pressure, neurotransmission, and platelet aggregation. 4,5 These interesting molecules thus bridge fatty acid-derived signaling with nitric oxide-mediated signaling. More recent work shows that (E)-9-and (E)-10-nitrooctadec-9-enoic acids (nitrated oleic acids, OA-NO 2 ) occur with a Correspondence to: S. Bruce King, kingsb@wfu.edu. Supporting Information Available: Full experimental details for the preparation of all intermediates and products, as well as complete spectroscopic and analytical data for all characterized compounds. Copies of 1 H and 13 C NMR spectra for 1, 2, 4, 6, 7, 12, and 13 are also included. This material is available free of charge via the Internet at http://pubs.acs.org. Current methods for the synthesis of these nitrated fatty acids involve the modification of previous nitroselenylation strategies used to synthesize conjugated nitroalkenes. 7,8 Alternatively, addition of nitronium tetrafluoroborate to an unsaturated fatty acid or fatty acid hydroperoxide also forms nitrated fatty acids. 9 These non-specific procedures form regioisomeric mixtures of nitro alkene products that require multiple purification steps. More importantly, these non-specific syntheses prevent strict analysis of the structural requirements for the biological activity of these unique molecules. Here we report the first regio-and stereospecific syntheses of (E)-9-nitro-octadec-9-enoic acid (1) and (E)-10-nitrooctadec-9-enoic acid (2) and show that these nitrated lipids spontaneously release nitric oxide. NIH Public AccessScheme 1 describes the retrosynthetic strategy for ...

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Nitroalkane synthesis. A convenient method for aldehyde reductive nitromethylation

Cited by 61 publications

References 16 publications

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones

Synthesis and spin trapping kinetics of new alkyl substituted cyclic nitrones

Regio- and Stereospecific Syntheses and Nitric Oxide Donor Properties of (E)-9- and (E)-10-Nitrooctadec-9-enoic Acids

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Nitroalkane synthesis. A convenient method for aldehyde reductive nitromethylation

Cited by 61 publications

References 16 publications

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.02,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.02,6]heptan-3-ones from cyclopentenones

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.02,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.02,6]heptan-3-ones from cyclopentenones

Synthesis and spin trapping kinetics of new alkyl substituted cyclic nitrones

Regio- and Stereospecific Syntheses and Nitric Oxide Donor Properties of (E)-9- and (E)-10-Nitrooctadec-9-enoic Acids

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Product

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Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones

Nitro-olefin bicycloannulation: one-step synthesis of tricyclo[3.2.1.0^2,7]octan-6-ones from cyclohexenones and of tricyclo[2.2.1.0^2,6]heptan-3-ones from cyclopentenones