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.
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TL;DR: An acidity- and temperature-dependent chemoselective glycosylation of silyl-protected rhamnals with alcohols has been revealed, allowing facile and practical access to both 2,3-unsaturated rhamnosides with excellent yields and high α-stereoselectivity.
17 citations
TL;DR: This allyloxycarbenium ion was further exploited in the Ferrier rearrangement to afford unsaturated nitrogen-containing C -aryl glycosides and C -alkyl glycoside under superacid and flow conditions respectively.
Abstract: The transformation of glycals into 2,3-unsaturated glycosyl derivatives, reported by Ferrier in 1962, is supposed to involve an α,β unsaturated glycosyl cation, an elusive ionic species that has still to be observed experimentally. Herein, while combination of TfOH and flow conditions failed to observe this ionic species, its extended lifetime in superacid solutions allowed its characterization by NMR-based structural analysis supported by DFT calculations. This allyloxycarbenium ion was further exploited in the Ferrier rearrangement to afford unsaturated nitrogen-containing C-aryl glycosides and C-alkyl glycosides under superacid and flow conditions, respectively.
17 citations
TL;DR: A review of 1,2-cyclopropyl car-bohydrates can be found in this article, where a wide variety of products are obtained depending on the functionality attached to the cyclopropane and the promoter (Lewis acid, Br o nsted acid, halophile or base).
Abstract: Addition of a carbene to a glycal is the prominent method for the synthesis of 1,2-cyclopropyl car- bohydrates. This incorporation of a cyclopropane into a carbohydrate scaffold enables divergent reactivity, with the two main classes being ring expansion and cleavage to 2- C -branched carbohydrates. A wide variety of products are obtained depending on the functionality attached to the cyclopropane (none or ester or hal- ogens) and the promoter (Lewis acid, Br o nsted acid, halophile or base) used in the reaction. This article reviews progress in the synthesis and reactions of 1,2-cyclopropyl carbohydrates since 2000 and discloses efforts by our group in the area.
16 citations
TL;DR: In this paper, 5-hydroxymethylfurfural was conveniently synthesized by dehydration of D-fructose in a good yield, and it was used to further build bioactive derivatives from 2,3-unsaturated glyco...
16 citations
TL;DR: A carbon-Ferrier rearrangement on glycals has been performed by using ceric ammonium nitrate to obtain products in moderate to good yields with high selectivity and for the synthesis of a orthogonally protected 2-amino-2-deoxy-C-glycoside.
Abstract: A carbon-Ferrier rearrangement on glycals has been performed by using ceric ammonium nitrate to obtain products in moderate to good yields with high selectivity. The versatility of this method has been demonstrated by applying it to differently protected glycals and by employing several nucleophiles. The obtained C-allyl glycoside has been utilized for the synthesis of a orthogonally protected 2-amino-2-deoxy-C-glycoside.
16 citations
References
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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
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
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.
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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
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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