Showing papers on "Ferrier rearrangement published in 2016"
TL;DR: An efficient method has been developed to generate a diverse array of indolizidines and quinolizidine from readily available aminaloalkynes via a gold(I)-catalyzed hydroaminaloxylation and Petasis-Ferrier rearrangement cascade.
21 citations
23 Sep 2016
TL;DR: The Ferrier rearrangement is a well-established synthetic procedure with ample use in the fields of carbohydrate and organic chemistry as discussed by the authors, and it has been extensively reviewed in the literature.
Abstract: The transformation of glycals (1,2-unsaturated cyclic carbohydrate derivatives) into 2,3-unsaturated glycosyl derivatives, currently termed Ferrier rearrangement, is a well-established synthetic procedure with ample use in the fields of carbohydrate and organic chemistry. This article highlights the developments in the Ferrier rearrangement published in the literature since the last review, in 2013, to early 2016.
19 citations
TL;DR: A one-pot cyclization sequence involving the Ferrier and Povarov-like reactions in the synthesis of novel pentacyclic N-heterocycles: benzopyran-fused pyranoquinolines is reported.
Abstract: The Ferrier rearrangement and the Povarov reaction have proven indispensable tools in carbohydrate chemistry and the synthesis of N-heterocycles, respectively. We hereby report a one-pot cyclization sequence involving the Ferrier and Povarov-like reactions in the synthesis of novel pentacyclic N-heterocycles: benzopyran-fused pyranoquinolines. The reaction entails three component condensation of a glycal with a variety of anilines and 2-hydroxybenzaldehydes under Lewis acid catalysis to yield the title compounds in 4–24 hours of reaction time, in moderate to high yields and excellent diastereoselectivity. Of the Lewis acid catalysts deployed [Sc(OTf)3, Al(OTf)3, Cu(OTf)2, CuOTf, I2, InCl3, and La(OTf)3] in various solvents (acetonitrile, THF, dichloromethane, 1,2-dichloroethane and diethyl ether) at room and elevated temperatures, Sc(OTf)3 (10 mol%) in acetonitrile at 70 °C gave the best results, with excellent diastereoselectivity. CAN-mediated oxidative ring opening of the pentacyclic N-heterocycle gave the corresponding enantiometrically pure chromenoquinoline bearing a pendant sugar moiety.
16 citations
TL;DR: Since these first reports, the ‘Petasis-Ferrier rearrangement’ has represented a vibrant area of research and innovation for organic chemists, and with numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established.
Abstract: In the mid-1990s, Petasis reexamined a promising but infrequently used rearrangement strategy, the so-called Ferrier-type-II reaction, and provided it with a modern update. Previously, Ferrier had developed a strategy where carbohydrate derivatives would undergo a fragmentation/aldol-type recombination sequence, generating a carbocycle, albeit under the promotion of stoichiometric mercury salts. Petasis' new variant showed the promise to effectively and stereoselectively convert a range of cyclic vinyl acetals to useful tetrahydrofurans and tetrahydropyrans, using less toxic promoters. Since these first reports, the 'Petasis-Ferrier rearrangement' has represented a vibrant area of research and innovation for organic chemists. With numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established. Recent developments have extended the reaction to a broader synthetic context, allowing for in situ generation of rearrangement substrates and more liberal interpretation of what fragmentation/recombination reactions warrant the designation of a Petasis-Ferrier rearrangement.
16 citations
TL;DR: In this article, a series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-acetyl-d -glucal, 3, 4,6 -tri-o-benzyl- d -glocal, and 3.4-di-Oacetyl -l -rhamnal under mild reaction conditions in good yields and high anomeric selectivities.
9 citations
TL;DR: A magnetic core-shell solid-acid catalyst Fe3O4@C-SO3H was used for synthesis of O-2,3-unsaturated glycosides through Ferrier rearrangement as mentioned in this paper.
Abstract: A magnetic core-shell solid-acid catalyst Fe3O4@C-SO3H was studied for synthesis of O-2,3-unsaturated glycosides through Ferrier rearrangement. The donors include 3,4,6-tri-O-acetyl- d -glucal and 3,4-di-O-acetyl- l -rhamnal. The acceptors consist of primary alcohols, secondary alcohols, tert-butanol, unsaturated alcohols, halogenated alcohol, sterol, sugars, and phenols. O-2,3-Unsaturated glycosides were obtained rapidly ( 5:1 to 19:1). Moreover, the catalyst can be easily separated from the reaction with an external magnetic force and reused for a minimum of five times without any significant decrease in the yields of the products after every recycle, suggesting it a promising green catalyst in 2,3-unsaturated glycosides syntheses.
9 citations
TL;DR: In this article, a highly efficient method to afford 2,3-unsaturated glycosides was described, in the presence of Hafnium(IV) triflate, in which a variety of 2, 3unsaturated- O - and S -glycosides have been obtained by stereoselective glycosylation of 3,4,6-tri-O -acetyl-d -glucal and hexa-O −acetyl -d -lactal with various acceptors in good isolated yields.
8 citations
TL;DR: A concise synthesis of asymmetrically substituted scyllo-inositol starting from inexpensive d -glucose is presented, which capitalizes on Ferrier rearrangement of vinyl acetate and stereoselective reduction of the resultant ketone to establish the scYllo- inositol core.
6 citations
Patent•
16 Nov 2016
TL;DR: In this paper, a synthetic method of 5-hydroxymethyl furfural doped 2,3-unsaturated glucoside was described, in which a Ferrier rearrangement reaction was carried out on D-fructose in dimethyl sulfoxide by taking FeCl3 6H2O/C as a catalyst.
Abstract: The invention discloses a synthetic method of 5-hydroxymethyl furfural doped 2,3-unsaturated glucoside. The synthetic method is characterized in that a Ferrier rearrangement reaction is carried out on D-fructose in dimethyl sulfoxide by taking FeCl3 6H2O/C as a catalyst, prepared 5-hydroxymethyl furfural is not separated and is directly used as a receptor in the next Ferrier rearrangement reaction, and a one-pot reaction is carried out on the receptor and 2,3-unsaturated saccharides which are used as a donor to synthetize 2,3-unsaturated glucoside. Compared with the prior art, the synthetic method disclosed by the invention has the advantages that two reactions are used as the one-pot reaction to synthetize the 2,3-unsaturated glucoside, cyclic utilization of the catalyst is up to at least three times, the catalyst still has relative high catalytic activity, the technology is simple, the operation is convenient, the yield is high, the production cost is low, and the synthetic method is an environment-friendly, economical and efficient novel method for synthetizing the 2,3-unsaturated glucoside and has a good application prospect.
3 citations
TL;DR: In this paper, an efficient method has been developed to generate a diverse array of indolizidines and quinolizidine from readily available aminaloalkynes via a gold(I)-catalyzed hydroaminaloxylation and Petasis-Ferrier rearrangement cascade.
Abstract: An efficient method has been developed to generate a diverse array of indolizidines and quinolizidines from readily available aminaloalkynes via a gold(I)-catalyzed hydroaminaloxylation and Petasis–Ferrier rearrangement cascade. The method enabled a formal synthesis of (±)-antofine.
1 citations
TL;DR: In this paper, a one-pot cyclization sequence involving the Ferrier and Povarov-like reactions in the synthesis of novel pentacyclic N-heterocycles: benzopyran-fused pyranoquinolines.
Abstract: The Ferrier rearrangement and the Povarov reaction have proven indispensable tools in carbohydrate chemistry and the synthesis of N-heterocycles, respectively. We hereby report a one-pot cyclization sequence involving the Ferrier and Povarov-like reactions in the synthesis of novel pentacyclic N-heterocycles: benzopyran-fused pyranoquinolines. The reaction entails three component condensation of a glycal with a variety of anilines and 2-hydroxybenzaldehydes under Lewis acid catalysis to yield the title compounds in 4–24 hours of reaction time, in moderate to high yields and excellent diastereoselectivity. Of the Lewis acid catalysts deployed [Sc(OTf)3, Al(OTf)3, Cu(OTf)2, CuOTf, I2, InCl3, and La(OTf)3] in various solvents (acetonitrile, THF, dichloromethane, 1,2-dichloroethane and diethyl ether) at room and elevated temperatures, Sc(OTf)3 (10 mol%) in acetonitrile at 70 °C gave the best results, with excellent diastereoselectivity. CAN-mediated oxidative ring opening of the pentacyclic N-heterocycle gave the corresponding enantiometrically pure chromenoquinoline bearing a pendant sugar moiety.
TL;DR: Petasis-Ferrier rearrangement has represented a vibrant area of research and innovation for organic chemists as discussed by the authors, with numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established.
Abstract: In the mid-1990s, Petasis reexamined a promising but infrequently used rearrangement strategy, the so-called Ferrier-type-II reaction, and provided it with a modern update. Previously, Ferrier had developed a strategy where carbohydrate derivatives would undergo a fragmentation/aldol-type recombination sequence, generating a carbocycle, albeit under the promotion of stoichiometric mercury salts. Petasis' new variant showed the promise to effectively and stereoselectively convert a range of cyclic vinyl acetals to useful tetrahydrofurans and tetrahydropyrans, using less toxic promoters. Since these first reports, the 'Petasis-Ferrier rearrangement' has represented a vibrant area of research and innovation for organic chemists. With numerous applications in complex natural product total synthesis, the utility of the reaction has been resoundingly established. Recent developments have extended the reaction to a broader synthetic context, allowing for in situ generation of rearrangement substrates and more liberal interpretation of what fragmentation/recombination reactions warrant the designation of a Petasis-Ferrier rearrangement.
TL;DR: In this article, a method to prepare 3-alkoxyindanones efficiently by gold-catalyzed tandem cycloisomerization/Petasis-Ferrier rearrangement from ortho-ethynylarylaldehydes with alcohols is described.
Abstract: A method to prepare 3-alkoxyindanones efficiently by gold-catalyzed tandem cycloisomerization/Petasis–Ferrier rearrangement from ortho-ethynylarylaldehydes with alcohols is described. The reaction was accomplished in moderate to excellent yields under mild reaction conditions and also offers a convenient synthetic route to 3-alkoxycyclopentenones.
TL;DR: In this article, a highly efficient method to afford 2,3-unsaturated glycosides was described, in the presence of Hafnium(IV) triflate, in which a variety of 2, 3unsaturated- O - and S -glycosides have been obtained by stereoselective glycosylation of 3,4,6-tri-O -acetyl-d -glucal and hexa-O −acetyl -d -lactal with various acceptors in good isolated yields.
Abstract: A highly efficient method to afford 2,3-unsaturated glycosides was described. In the presence of Hafnium(IV) triflate, a variety of 2,3-unsaturated- O - and S -glycosides have been obtained by stereoselective glycosylation of 3,4,6-tri- O -acetyl- d -glucal and hexa- O -acetyl- d -lactal with various acceptors in good isolated yields.
TL;DR: In this article, two strategies were considered for the synthesis of 2,3-unsaturated O-glucosyl-1,2, 3-triazoles using Ferrier rearrangement.
Abstract: Two strategies were considered for the synthesis of 2,3-unsaturated O-glucosyl-1,2,3-triazoles. The first, involving reaction between tri-O-acetyl- d -glucal and triazole alcohols gave no stereoselectivity. A second strategy provided 2,3-unsaturated O-glycosides from glycals and alkynols through a Ferrier rearrangement; this method, employing montmorillonite K-10 doped with iron(III) chloride hexahydrate in dichloromethane afforded new glycosides in good to excellent yields within short times and with high α-stereoselectivities. Subsequently, the glucosides were coupled with 2-azido-1,4-naphthoquinone to produce a new series of 1,2,3-1H-triazolyl O-glucoside derivatives through a click reaction.
TL;DR: In this paper, a series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-acetyl-d -glucal, 3, 4,6 -tri-o-benzyl- d -glocal, and 3.4-di-Oacetyl -l -rhamnal under mild reaction conditions in good yields and high anomeric selectivities.
Abstract: By using Gd(OTf)3 as the catalyst, synthesis of 2,3-unsaturated-glycosides has been performed by Ferrier Rearrangement. A series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-acetyl- d -glucal, 3,4,6-tri-O-benzyl- d -glucal, and 3,4-di-O-acetyl- l -rhamnal under mild reaction conditions in good yields and high anomeric selectivities.