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Journal ArticleDOI

Recent Developments in the Ferrier Rearrangement

01 Nov 2013-European Journal of Organic Chemistry (John Wiley & Sons, Ltd)-Vol. 2013, Iss: 32, pp 7221-7262
TL;DR: A review of recent developments in the use of promoters for the Ferrier rearrangement of O-, N-, C- and S-nucleophiles with glycals can be found in this paper.
About: This article is published in European Journal of Organic Chemistry.The article was published on 2013-11-01. It has received 121 citations till now. The article focuses on the topics: Ferrier rearrangement & Ferrier carbocyclization.
Citations
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Journal ArticleDOI
TL;DR: FeFeCl3/C was used as an efficient and convenient promoter for glycosylation through Ferrier-type rearrangement of 3,4,6-tri-Obenzyl-D-glucal as mentioned in this paper.

2 citations

Book ChapterDOI
01 Jan 2020
TL;DR: The Ferrier-Nicholas reaction has shown to be particularly useful when applied to carbohydrate derivatives, such as C-alkynyl glycosides and pyranose ring-opening ring-recyclization leading to medium-sized oxacycles.
Abstract: The complexation of alkynes to form dicobalt hexacarbonyl derivatives facilitates the formation, under acid catalysis, of highly stabilized propargylic cations whose reaction with nucleophiles to form propargylic compounds, currently known as the Nicholas reaction, has found ample use in organic synthesis. This transformation has shown to be particularly useful when applied to carbohydrate derivatives. In this chapter, we provide a brief overview on this subject pioneered by early contributions from Isobe’s research group. Thus, carbohydrate-derived dicobalt hexacarbonyl complexes have been used in the epimerization of C-alkynyl glycosides, pyranose ring-opening nucleophile trapping reactions, pyranose ring-opening ring-recyclization leading to medium-sized oxacycles, glycosylation strategies, C-glycosylation, and pyranose to carbocycle transformations, among others. Finally, contributions from our research group focusing on the synthetic applications of Ferrier-Nicholas cations are also presented.

2 citations

Journal ArticleDOI
TL;DR: A β-C-glycosylation of C- glycosides is described, which results in the formation of a new C- Glycosidic bond stereoselectively in the presence of Na6(CO3)(SO4)SO4 and Na2SO4.
Abstract: Despite the increased importance of C-glycosides in biochemistry, strategy to forge C-glycosidic bond stereoselectively is inherently more challenging than the O- and N- counterparts. We describe here a β-C-glycosylation of...

2 citations

Journal ArticleDOI
TL;DR: In this paper, a two-step methodology was developed for the synthesis of chiral pyrroles from 2−nitroglycals via Ferrier rearrangement and Barton-Zard reaction under mild conditions without transition metal catalysts.
Abstract: In this study, a two‐step methodology was developed for the synthesis of chiral pyrroles from 2‐nitroglycals via Ferrier rearrangement and Barton‐Zard reaction under mild conditions without transition metal catalysts. The Ferrier rearrangement reaction of 2‐nitro‐glycals and a series of O‐nucleophiles proceeded smoothly in the presence of N‐heterocyclic carbene (NHC) catalyst and K2CO3 which allowed the highly stereoselective synthesis of the diverse 2‐nitro‐2,3‐unsaturated glycosides in excellent yields. Subsequently, the rearrangement products were conveniently transformed into the desired chiral pyrroles by [3+2] cycloaddition (Barton‐Zard reaction) with isocyanoacetate in the presence of Cs2CO3. One‐pot strategy was also successfully demonstrated for the gram‐scale synthesis of one chiral pyrrole. This is the first report of stereoselective conversion from 2‐nitroglycals to chiral pyrrole.

2 citations

Journal ArticleDOI
TL;DR: Glycals have been extensively utilized as a versatile building block in the constructions of C-glycosides, branched sugars, and the total synthesis of natural products and biologically potent molecules as discussed by the authors .
Abstract: Glycals have been extensively utilized as a versatile building block in the constructions of C-glycosides, branched sugars, and the total synthesis of natural products and biologically potent molecules. The versatility of glycals can be attributed to their easy availability and the presence of endocyclic ring oxygen in conjugation with the double bond. The inbuilt chirality further enhances its applicability in the chiral pool synthesis of natural products and pharmaceuticals. In this review, we have summarized the development made in the total synthesis of natural products and some medicinally relevant molecules from glycals.

1 citations

References
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Journal ArticleDOI
TL;DR: A novel regiospecific copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes to azides on solid-phase is reported, and the X-ray structure of 2-azido-2-methylpropanoic acid has been solved, to yield structural information on the 1, 3-dipoles entering the reaction.
Abstract: The cycloaddition of azides to alkynes is one of the most important synthetic routes to 1H-[1,2,3]-triazoles. Here a novel regiospecific copper(I)-catalyzed 1,3-dipolar cycloaddition of terminal alkynes to azides on solid-phase is reported. Primary, secondary, and tertiary alkyl azides, aryl azides, and an azido sugar were used successfully in the copper(I)-catalyzed cycloaddition producing diversely 1,4-substituted [1,2,3]-triazoles in peptide backbones or side chains. The reaction conditions were fully compatible with solid-phase peptide synthesis on polar supports. The copper(I) catalysis is mild and efficient (>95% conversion and purity in most cases) and furthermore, the X-ray structure of 2-azido-2-methylpropanoic acid has been solved, to yield structural information on the 1,3-dipoles entering the reaction. Novel Fmoc-protected amino azides derived from Fmoc-amino alcohols were prepared by the Mitsunobu reaction.

7,397 citations

Journal ArticleDOI
TL;DR: In this article, a reagent formed by combining diethyl azodicarboxylate (DEAD) and triphenylphosphine (TPP) could be utilized in the intermolecular dehydration between an alcohol and various acidic components such as carboxylic acids, phosphoric diesters, imides, and active methylene compounds.
Abstract: The reagent formed by combining diethyl azodicarboxylate (DEAD) and triphenylphosphine (TPP) could be utilized in the intermolecular dehydration between an alcohol and various acidic components such as carboxylic acids, phosphoric diesters, imides, and active methylene compounds. By the use of DEAD and TPP, diols and hydroxy acids gave cyclic ethers and lactones, respectively. The reaction of nucleosides with DEAD and TPP afforded triphenylphosphoranylnucleosides. Alcohols reacted with 2,6-di-t-butyl-4-nitrophenol in the presence of DEAD and TPP to give aci-nitroesters which converted into the corresponding carbonyl compounds.

3,209 citations

Journal ArticleDOI
TL;DR: The copper-(I)-catalyzed 1,2,3-triazole formation from azides and terminal acetylenes is a particularly powerful linking reaction, due to its high degree of dependability, complete specificity, and the bio-compatibility of the reactants.

2,882 citations

Journal ArticleDOI
TL;DR: In this paper, the authors show how in der Natur am haufigsten vorkommenden Verbindungen, so fallt auf, dass the Bildung von Kohlenstoff-Heteroatom-Bindungen gegenuber der von KHO-Kohlenstoffs-KHO-Bindingsen deutlich bevorzugt is, and das Medium naturlicher Reaktionen zumeist Wasser ist.
Abstract: Betrachtet man die in der Natur am haufigsten vorkommenden Verbindungen, so fallt auf, dass die Bildung von Kohlenstoff-Heteroatom-Bindungen gegenuber der von Kohlenstoff-Kohlenstoff-Bindungen deutlich bevorzugt ist Da zum einen Kohlendioxid die Basisverbindung der Natur ist und andererseits das Medium naturlicher Reaktionen zumeist Wasser ist, uberrascht dies sicherlich nicht Nucleinsauren, Proteine und Polysaccharide sind polymere Kondensationsprodukte kleiner Untereinheiten, die durch Kohlenstoff-Heteroatom-Bindungen verknupft sind Sogar die etwa 35 Baueinheiten, aus denen diese essentiellen Verbindungen bestehen, enthalten nicht mehr als sechs aufeinander folgende C-C-Bindungen, sieht man einmal von den drei aromatischen Aminosauren ab Mit der Natur als Vorbild richteten wir unser Interesse auf die Entwicklung leistungsfahiger, gut funktionierender und selektiver Reaktionen fur die effiziente Synthese neuartiger nutzlicher Verbindungen sowie kombinatorischer Bibliotheken mittels Heteroatomverknupfungen (C-X-C) Diese Synthesestrategie nennen wir „Click-Chemie“ Click-Chemie ist durch eine Auswahl einiger weniger nahezu idealer Reaktionen charakterisiert, mit all ihren Grenzen und Moglichkeiten In diesem Beitrag werden zum einen die strengen Kriterien, die Reaktionen erfullen mussen, um die Bezeichnung „Click-Chemie“ zu verdienen, definiert, zum anderen werden Beispiele fur molekulare Strukturen gegeben, die mit dieser spartanischen, aber dennoch leistungsfahigen Synthesestrategie leicht hergestellt werden konnen

1,380 citations

Journal ArticleDOI
TL;DR: An overview of the mechanism of this remarkable reaction is presented as a means to explain the myriad of experimental results, particularly the various methods of catalyst generation, solvent and substrate effects, and choice of base or ligand as discussed by the authors.

1,319 citations