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: In this article, a highly efficient C-glycosylation method was developed by using catalytic Zn(OTf)2 for the synthesis of 2,3-unsaturated Cglycosides.
Abstract: A highly efficient C-glycosylation method was developed by using catalytic Zn(OTf)2 for the synthesis of 2,3-unsaturated C-glycosides. The scope of the protocol was well illustrated with different substituted glycals and nucleophiles comprising allyltrimethylsilane, triethylsilane, trimethylsilyl cyanide, trimethylsilyl azide, trimethylaluminum, trimethylsilyl phenylacetylene and heterocycles such as thiophene and furan. The present method is mild enough to incorporate C-glycoside linkages in a disaccharide donor as well.
26 citations
TL;DR: Two one-pot oxidative annulative approaches to spiroacetal synthesis are described, which provide convergent routes to common subunits in natural products, medicinal agents, and chemical libraries under mild reaction conditions.
24 citations
TL;DR: A flexible approach for the incorporation of CF3 units into a predefined site of electron-rich alkenes that exploits the regiocontrolled introduction of an iodine handle and subsequent trifluoromethylation of the C(sp2)-I bond using fluoroform-derived "ligandless" CuCF3 is presented.
Abstract: We herein present a flexible approach for the incorporation of CF3 units into a predefined site of electron-rich alkenes that exploits the regiocontrolled introduction of an iodine handle and subsequent trifluoromethylation of the C(sp2)–I bond using fluoroform-derived “ligandless” CuCF3. The broad substrate scope and functional group tolerance together with the scalability and purity of the resulting products enabled the controlled, late-stage synthesis of single regioisomers of complex CF3-scaffolds, such as sugars, nucleosides (antivirals), and heterocycles (indoles and chromones), with potential for academic and industrial applications.
24 citations
TL;DR: The Pd-π-allyl intermediate in an electron-rich glycal system with poor reactivity is employed as an efficient glycosyl donor and may provide an access to complex oligosaccharides.
Abstract: The Pd-π-allyl intermediate in an electron-rich glycal system with poor reactivity is employed as an efficient glycosyl donor. Starting from glucal derived carbonate, various O-glycosides were formed via a palladium-catalyzed reaction through a tandem decarboxylation, proton abstraction, and nucleophilic addition, in good yields with excellent selectivity. Iterative glycosylation with the same strategy may provide an access to complex oligosaccharides.
22 citations
TL;DR: The operational simplicity and robustness of this system enables the efficient, late-stage incorporation of C2F5 units into a variety of (hetero)aryl and complex alkenyl halides such as glycals, nucleosides, and nucleobases.
Abstract: Pentafluoroethylation of unactivated C(sp2)-X bonds (X = I, Br) using a storable, "ligandless" CuC2F5 reagent prepared by controlled self-condensation of ready available TMSCF3-derived CuCF3 has been developed. A thorough analysis by 19F NMR and ESI-MS revealed the nature of this reagent in solution. The operational simplicity and robustness of this system enables the efficient, late-stage incorporation of C2F5 units into a variety of (hetero)aryl and complex alkenyl halides such as glycals, nucleosides, and nucleobases.
22 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.
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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.
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