Total synthesis of biologically important amino sugars via thenitroaldol reaction

doi:10.1016/S0040-4039(00)94865-2

Tetrahedron Letters

Volume 26, Issue 10, 1985, Pages 1261-1264

https://doi.org/10.1016/S0040-4039(00)94865-2 Get rights and content

Abstract

Aldol condensation between $O$ -benzyl D-or L-lactaldehyde and alkyl 3-nitropropionates in the presence of various catalysts leads to stereoisomeric nitroaldol products which can be transformed into aminodeoxy hexoses in the D- or L-series.

References (16)

A. Bargiotti et al.
Carbohydr. Res.
(1982)
T. Yamaguchi et al.
Carbohydr. Res.
(1977)
D. Horton et al.
Carbohydr. Res.
(1976)
B. Fraser-Reid et al.
J.C.S Chem. Comm.
(1983)
G.J. Mcgarvey et al.
J. Carbohyd. Chem.
(1984)
T. Hiyama et al.
Tetrahedron Lett.
(1984)
C. Fuganti et al.
J. Org. Chem.
(1983)
C.H. Heathcock et al.
Tetrahedron Lett.
(1983)
L.E. Overman et al.
J. Am. Chem. Soc.
(1984)
D. Seebach et al.
Helv. Chim. Acta
(1982)
F. Arcamone et al.
J. Am. Chem. Soc.
(1964)
K. Mislow et al.
J. Am. Chem. Soc.
(1962)
S.J. Abbott et al.
J. Am. Chem. Soc.
(1979)
S. Umezawa
Carbohydrates, Organic Series Two
(1976)
S. Hanessian et al.
The Carbohydrates
(1970)
V. Sharon
(1975)

There are more references available in the full text version of this article.

Cited by (92)

Sialyl Lewis<sup>X</sup> glycomimetics bearing an extended anionic chain targeting E- and P- selectin binding sites
2024, Bioorganic and Medicinal Chemistry
Neutrophil binding to vascular P- and E-selectin is the rate-limiting step in the recruitment of immune cells to sites of inflammation. Many diseases, including sickle cell anemia, post-myocardial infarction reperfusion injury, and acute respiratory distress syndrome are characterized by dysregulated inflammation. We have recently reported sialyl Lewis^x analogues as potent antagonists of P- and E-selectin and demonstrated their in vivo immunosuppressive activity. A key component of these molecules is a tartrate diester that serves as an acyclic tether to orient the fucoside and the galactoside moiety in the required gauche conformation for optimal binding. The next stage of our study involved attaching an extended carbon chain onto one of the esters. This chain could be utilized to tether other pharmacophores, lipids, and contrast agents in the context of enhancing pharmacological applications through the sialyl Lewis^x / receptor-mediated mechanism. Herein, we report our preliminary studies to generate a small library of tartrate based sialyl Lewis^x analogues bearing extended carbon chains. Anionic charged chemical entities are attached to take advantage of proximal charged amino acids in the carbohydrate recognition domain of the selectin receptors. Starting with a common azido intermediate, synthesized using copper-catalyzed Huisgen 1,3-dipolar cycloadditions, these molecules demonstrate E- and P-selectin binding properties.
Highly efficient and recyclable chiral Pt nanoparticle catalyst for enantioselective hydrogenation of activated ketones
2018, Catalysis Communications
Citation Excerpt :
Chiral secondary alcohols are very important intermediates and auxiliaries in the asymmetric synthesis chemistry. For example, chiral α-hydroxy acetals not only can be converted to chiral 1,2-diols, chiral β-amino alcohols and chiral aldol derivatives [1–3], but also are necessary chiral building blocks for synthesis of lipoxine A [4], rhodinose [5], rocellaric acid [6], grayanotoxins [7] and amino sugars [8]. Meanwhile, chiral 1,2-diols are crucial components for synthesis of insect pheromones [9], δ-lactones [10], β-lactone esterase inhibitors [11], especially for anti-HIV pharmaceutical tenofovir [12] and many other biologically active substances [13].
Thermoregulated phase-separable chiral Pt nanoparticle catalyst exhibited excellent ee (>99%) in the enantioselective hydrogenation of activated ketones for preparing chiral α-hydroxy acetals and chiral 1,2-diols. More importantly, the chiral catalyst could be easily separated by phase separation and directly reused in the next cycle without any loss in catalytic activity and enantioselectivity, even in the gram-scale reaction. The leaching of Pt was under the detection limit of the instrument.
Stereoselective reactions of nitro compounds in the synthesis of natural compound analogs and active pharmaceutical ingredients
2016, Tetrahedron
Citation Excerpt :
Thus obtained synthetically versatile β-nitroalcohols 118 and 119 were afterwards stereoselectively converted to a pyrroloisoquinoline derivative 120 or (+)-Spisulosine, respectively (Scheme 49). Pyrroloisoquinoline ring system forms the central skeleton of the Erythrina alkaloid group.107 ( +)-Spisulosine ES285 was isolated from Spisula polynyma, and has been shown to possess long-lasting antitumor cytotoxic activity on the nanomolar scale, both in vitro and in vivo.108
Cyclopropanation of 1,2-dibromoethylphosphonate: A synthesis of β-aminocyclopropylphosphonic acid and derivatives
2014, Tetrahedron Letters
Diethyl (1,2-dibromoethyl)phosphonate was found to undergo cyclopropanation with nitromethane in good yield. The resulting trans β-nitrocyclopropylphosphonate was converted to the trans N-protected aminocyclopropylphosphonate through a reduction–protection sequence. Subsequent hydrolysis gave the free β-aminocyclopropylphosphonic acid without any formation of ring-opening byproduct. Cyclopropanation of 1,2-dibromoethylphosphonates with nitroalkanes and their reduction are also discussed.
Synthesis, spectral characterization and crystal structure of Ni(II) pyridoxal thiosemicarbazone complexes and their recyclable catalytic application in the nitroaldol (Henry) reaction in ionic liquid media
2014, Polyhedron
Citation Excerpt :
Shibasaki reported the first asymmetric version of the nitroaldol reaction in 1992 [33]. Since then various transition metals such as Cu [34], Zn [35], Co [36], Cr [37], Pd [38], Ru [39] and rare metals [40] have been applied to the catalytic version of the nitroaldol reaction. In contrast, nickel, an attractive surrogate for precious metals in terms of its abundance and low cost, has not been investigated so far in the nitroaldol reaction.
The new square planar nickel(II) complexes 1, 2 and 3 have been synthesized from the reaction of [NiCl₂(PPh₃)₂] with the tridentate Schiff base ligand, pyridoxal thiosemicarbazone (L¹), pyridoxal N-methyl thiosemicarbazone (L²) and pyridoxal N-phenyl thiosemicarbazone (L³) respectively in ethanol. These complexes have been characterized by elemental analyses, IR, UV–Vis, ¹H NMR, ³¹P NMR and ESI-MS spectroscopy. The molecular structure of the complex [Ni(L²)PPh₃] (2) was determined by single-crystal X-ray diffraction, which reveals a distorted square planar geometry around the nickel(II) ion. The nitroaldol reaction was studied in detail using the nickel(II) complexes as catalysts in a homogeneous solution formed by an ionic liquid and methanol. The effect of solvent, ionic liquid, time, temperature, catalyst loading and substituent of the ligand moiety on the reaction was also studied. The β-nitroalcohol products were obtained in good yields of up to 97%. A two step substrate addition mechanism was tentatively proposed based on ESI-MS spectral monitoring of the reaction mass.
Highly stereoselective De-Novo synthesis of protected 2-amino-3-C-methyl-2, 3-dideoxy-d-altrose
2010, Tetrahedron
Citation Excerpt :
Modified carbohydrates play an important role in the synthesis of antibodies,1 enzymes,2 and biologically active compounds.3 Recently we published the highly stereoselective synthesis of methyl-branched 2-amino-2-deoxy-aldoses from protected sugar aldehydes 1 (Scheme 1).4 Aldehydes 1 are elongated via introduction of the C-1–C-3 unit by homoaldol reaction of enantioenriched homoenolate reagent 2 to deliver enol carbamates 3.5

View all citing articles on Scopus

View full text

Total synthesis of biologically important amino sugars via thenitroaldol reaction

Abstract

Carbohydr. Res.

Carbohydr. Res.

Carbohydr. Res.

J.C.S Chem. Comm.

J. Carbohyd. Chem.

Tetrahedron Lett.

J. Org. Chem.

Tetrahedron Lett.

J. Am. Chem. Soc.

Helv. Chim. Acta

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Carbohydrates, Organic Series Two

The Carbohydrates