Synthesis of heterocyclic systems with a carbohydrate fragment

This paper reports new applications of the cathodically promoted addition of nitro compounds to the biomass-derived enone, levoglucosenone. A series of 2-substituted 1,3-dinitropropanes were found to undergo addition to levoglucosenone with generation of a tricyclic product containing a fused cyclohexane system. The reaction yields are good to excellent and are catalyzed by base (superoxide) generated electrochemically. Derivatives were prepared from 1,3-dinitropropanes with the following 2-substituents: 2-thienyl, 2-furyl, N-methyl-2-pyrryl, phenyl, 9-anthryl, and ferrocenyl. The structure of the derivative from 2-ferrocenyl-1,3-dinitropropane was established by X-ray crystallography, thus confirming the NMR-based stereochemical assignments of all of the other products.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.97.178.73 Downloaded on 2014-12-03 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 155.97.178.73 Downloaded on 2014-12-03 to IP

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“…acids, urea, thiourea, and guanidines, and 1,3-dicarbonyl compounds, compared to procedures that make use of chemical bases. [18][19][20] …”

Section: Resultsmentioning

confidence: 98%

“…17 Exceptions include the reaction of 1 with amides of ␣-nitrocarboxylic acids, 18 urea, thiourea, guanidines, 19 and 1,3-dicarbonyl compounds 20 giving fused tetrahydropyridone, pyrimidine, and pyran systems, respectively, by attachment at C(2) and C(4).…”

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confidence: 99%

Cathodically Promoted Stereoselective Addition of 1,3-Dinitro Compounds to Levoglucosenone

Niazimbetova

Evans

Incarvito

et al. 2000

J. Electrochem. Soc.

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“…Previous aza-Michael reactions to LGO are shown in Scheme 1. [15] An elegant heteroannulation was observed when aromatic bisnucleophiles were employed; [17,18] an initial conjugate addition followed by reaction at the carbonyl affords interesting N-containing scaf-Scheme 1. [14] Semenov, Evans and co-workers reported the aza-Michael addition of various azoles to LGO to give 3, which in some instances also formed a diol 4 resulting from carbonyl hydration (Scheme 1, B).…”

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confidence: 99%

“…Eiden and co-workers reported an aza-Michael addition of aniline and 2-bromoaniline to LGO to give 2a and 2b in poor yield (Scheme 1, A). [14][15][16][17][18] Eur. [15,16] The same paper reported the aza-Michael addition of imides and saccharin to LGO and that the yield of some reactions can be increased using cathodic electrolysis.…”

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confidence: 99%

“…Eiden and co-workers reported an aza-Michael addition of aniline and 2-bromoaniline to LGO to give 2a and 2b in poor yield (Scheme 1, A). [15] An elegant heteroannulation was observed when aromatic bisnucleophiles were employed; [17,18] an initial conjugate addition followed by reaction at the carbonyl affords interesting N-containing scaf-Scheme 1. [15,16] The same paper reported the aza-Michael addition of imides and saccharin to LGO and that the yield of some reactions can be increased using cathodic electrolysis.…”

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confidence: 99%

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Bio‐Based Chiral Amines via Aza‐Michael Additions to (–)‐Levoglucosenone Under Aqueous Conditions

et al. 2018

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Chiral amines are highly coveted within the fine‐chemical industry and sustainable synthetic methodologies for their production are of great value. By harnessing the chirality present in cellulose‐derived (–)‐levoglucosenone (LGO), several bio‐based sp3‐rich amines containing up to four chiral centres have been readily prepared under aqueous conditions without using any catalysts, ligands, auxiliaries or resolutions.

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ChemInform Abstract: Synthesis of Heterocyclic Systems with a Carbohydrate Fragment. Part 4. An Unusual Reactivity of Levoglucosenone with Respect to α‐ Aminoazoles and β‐Dicarbonyl Compounds.

Samet¹,

Yamskov²,

Уграк³

et al. 1997

ChemInform

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Levoglucosenone reacts with e~-aminoazoles to yield azolo [I,5-,.'lpyrimidine systems fused with a carbohydrate fragment. The reaction oocurs much more smoothly than in the case of other ct,l~-unsamrated ketones. The reactions of levogtucosenone with {3-dicarbonyl compounds (dimedone. barbituric acid) in the presence of a base results in the pyran ring closure, which has never been observed earlier in reactions of i3-dicarbonyt compounds with ,.;,..13-unsaturated ketones trader the conditions of basic catalysis. The structures of products were established by IR and NMR spectroscopy.

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Synthesis of heterocyclic systems with a carbohydrate fragment

Cited by 7 publications

References 7 publications

Cathodically Promoted Stereoselective Addition of 1,3-Dinitro Compounds to Levoglucosenone

Cathodically Promoted Stereoselective Addition of 1,3-Dinitro Compounds to Levoglucosenone

Bio‐Based Chiral Amines via Aza‐Michael Additions to (–)‐Levoglucosenone Under Aqueous Conditions

ChemInform Abstract: Synthesis of Heterocyclic Systems with a Carbohydrate Fragment. Part 4. An Unusual Reactivity of Levoglucosenone with Respect to α‐ Aminoazoles and β‐Dicarbonyl Compounds.

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