Synthesis of 1-aryl-(glycofurano)imidazolidine-2-thiones from new 2-(alkylamino)-2-deoxyhexoses

Pérez, Juan Manuel Sánchez; Albarran, Juan C. Palacios; Requejo, Jose L. Jimenez; Gonzalez, Martin Avalos; FERNANDEZ-BOLANOS, J. M.

doi:10.1016/0008-6215(84)85305-7

Cited by 14 publications

(9 citation statements)

References 26 publications

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“…Table shows the anomeric equilibrium data for several aldoses ( 72 – 76 ) , and Table those for 2-amino-2-deoxyaldoses and some derivatives ( 1 , 3 , 77 – 81 ). ,,, …”

Section: Resultsmentioning

confidence: 99%

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A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

Matamoros,

Pérez,

Light

et al. 2024

J. Org. Chem.

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The reverse anomeric effect is usually associated with the equatorial preference of nitrogen substituents at the anomeric center. Once postulated as another anomeric effect with explanations ranging from electrostatic interactions to delocalization effects, it is now firmly considered to be essentially steric in nature. Through an extensive research on aryl imines from 2-amino-2-deoxyaldoses, spanning nearly two decades, we realized that such substances often show an anomalous anomeric behavior that cannot easily be rationalized on the basis of purely steric grounds. The apparent preference, or stabilization, of the β-anomer takes place to an extent that not only neutralizes but also overcomes the normal anomeric effect. Calculations indicate that there is no stereoelectronic effect opposing the anomeric effect, resulting from the repulsion between electron lone pairs on the imine nitrogen and the endocyclic oxygen. Such data and compelling structural evidence unravel why the exoanomeric effect is largely inhibited. We are now confident, as witnessed by 2-iminoaldoses, that elimination of the exo-anomeric effect in the α-anomer is due to the formation of an intramolecular hydrogen bond between the anomeric hydroxyl and the iminic nitrogen, thereby accounting for a true electronic effect. In addition, discrete solvation may help justify the observed preference for the β-anomer.

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“…Table shows the anomeric equilibrium data for several aldoses ( 72 – 76 ) , and Table those for 2-amino-2-deoxyaldoses and some derivatives ( 1 , 3 , 77 – 81 ). ,,, …”

Section: Resultsmentioning

confidence: 99%

“… a Ref . b Ref . c pD = 4.2–5.8. d pD = 9.3–9.5 e Anomeric stabilization referred to cyclohexanol in kcal/mol. …”

Section: Resultsmentioning

confidence: 99%

A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

Matamoros,

Pérez,

Light

et al. 2024

J. Org. Chem.

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“…The preparation of aminonitriles 27-36 was performed as described previously [49][50][51][52][53][54][55][56] using the classical cyanohydrin synthesis, i.e., the addition of liquid hydrogen cyanide to a glycosylamine formed through reaction of the corresponding monosaccharide with an excess of ammonia, alkyl, or aryl amines. In general, isolation of the glycosylamine derivative, rather than the one-pot protocol, leads to a clean and high-yielding synthesis.…”

Section: Synthesis Of Acylated Derivativesmentioning

confidence: 99%

“…More recently, mass spectrometry of amino sugar aldononitrile acetate derivatives was used for isotope enrichment assessment of microbial residues in soil [35]. 2-Amino-2-deoxyaldononitriles and their N-alkyl and N-aryl derivatives are intermediates in the aminonitrile synthesis of 2-amino and 2-alkylamino-2deoxyaldoses [46][47][48][49][50][51][52][53][54][55][56], and they are generally obtained by reacting an aldose with excess of ammonia or an amine in anhydrous methanol/ethanol with subsequent addition of anhydrous hydrogen cyanide. However, unexpected by-products like aminoamides 4 and iminolactones 5 are sometimes obtained (Scheme 2) [57][58][59][60].…”

Section: Introductionmentioning

confidence: 99%

“…Peracyl-2-amino-2-deoxyaldononitriles can be generated through the acylation of 2amino-2-deoxyaldononitriles [49][50][51][52][53][54][55][56] and oximes of 2-amino-2-deoxyaldosas [61]. Such substances have been used for characterizing 2-amino-2-deoxyaldoses and their N-alkyl and Naryl derivatives, as well as synthons in the preparation of 1,2-diamino-1,2-dideoxyalditols [62], which are additional starting materials for the synthesis of polyhydroxyalkyl heterocycles.…”

Section: Introductionmentioning

confidence: 99%

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From Potential Prebiotic Synthons to Useful Chiral Scaffolds: A Synthetic and Structural Reinvestigation of 2-Amino-Aldononitriles

Matamoros,

Light,

Cintas

et al. 2024

Molecules

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This paper explores and revisits in detail the formation and characterization of sugar-based aminonitriles, whose ultimate origin can be traced to the interaction of biomolecules with cyanide. Although the synthesis and spectroscopic data of 2-amino-aldononitriles were reported long ago, there are both contradictory and confusing results among the published data. We have now addressed this concern through an exhaustive structural elucidation of acylated 2-amino- and 2-alkyl(aryl)amino-2-deoxyaldonitriles using mass spectrometry and FT-IR, FT–Raman, and NMR spectroscopies. Several structures could be unambiguously determined through single-crystal X-ray diffraction, which allowed us to correct other misassignments. Moreover, this study unveils how steric and electronic effects influence the acylation outcome of the amino, (alkyl, aryl)amino, or acetamido group at C-2. The chirality at the latter, which was assigned tentatively through optical rotation correlation, and hence the preferential threo stereochemistry generated during the cyanohydrin synthesis of 2-amino-2-deoxy aldononitriles have now been established with confidence.

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ChemInform Abstract: Synthesis of 1‐Aryl‐(glycofurano)imidazolidine‐2‐thiones from New 2‐(Alkylamino)‐2‐deoxyhexoses.

Pérez¹,

Albarran²,

Requejo³

et al. 1984

Chemischer Informationsdienst

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Synthesis of 1-aryl-(glycofurano)imidazolidine-2-thiones from new 2-(alkylamino)-2-deoxyhexoses

Cited by 14 publications

References 26 publications

A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

A True Reverse Anomeric Effect Does Exist After All: A Hydrogen Bonding Stereocontrolling Effect in 2-Iminoaldoses

From Potential Prebiotic Synthons to Useful Chiral Scaffolds: A Synthetic and Structural Reinvestigation of 2-Amino-Aldononitriles

ChemInform Abstract: Synthesis of 1‐Aryl‐(glycofurano)imidazolidine‐2‐thiones from New 2‐(Alkylamino)‐2‐deoxyhexoses.

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