- Y(OTf)3 as a highly efficient catalyst in Ferrier Rearrangement for the synthesis of O- and S-2,3-unsaturated glycopyranosides
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By using Y(OTf)3 as the catalyst, a series of 2,3-unsaturated-glucosides have been synthesized from 3,4,6-tri-O-acetyl-d-glucal, 3,4-di-O-acetyl-l-rhamnal, and 3,4,6-tri-O-benzyl-d-glucal under mild reaction conditions in good yields with high anomeric selectivities. It was found that, in this reaction, 3,4,6-tri-O-benzyl-d-glucal behaved differently from the other two glucals when it was reacted with phenol, O-benzyl glucoside instead of O-phenyl glucoside formed as the sole product. An explanation is given for this phenomenon.
- Chen, Peiran,Li, Shan
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- A Highly Efficient Magnetic Iron(III) Nanocatalyst for Ferrier Rearrangements
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A novel and highly efficient magnetic Fe 3 O 4 &at;C&at;Fe(III) core-shell catalyst, in which the carbon shell was prepared from lotus leaf, was fabricated. This nanocatalyst was successfully applied in the synthesis of a series of 2,3-unsaturated O- glycosides in excellent yields and with high selectivity, especially in the case of 2-halo O- glycosides, which differ in reactivity from nonsubstituted O- glycosides, but which have scarcely been explored before. Moreover, the catalyst could be easily separated from the reaction by the application of an external magnetic force and reused a minimum of five times without any significant decrease in the yields of the products. In addition, the reaction proceeded readily on a gram scale, which provides a bright prospect for future applications.
- Chen, Heshan,Ding, Zekun,Dong, Youxian,Guo, Hong,Jiang, Nan,Qiu, Saifeng,Xu, Xiaoxia,Zhang, Jianbo,Zhou, Le
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supporting information
p. 1419 - 1426
(2019/07/15)
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- Montmorillonite-catalyzed glysosylation of alcohols with glycals derived from galactose and glucose under microwave-induced reactions
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Montmorillonite K10-catalyzed glycosylation of alcohols with glycals obtained from galactose and glucose is performed efficiently using microwave irradiation with good anomeric selectivity.
- Yadav, Ram Naresh,Banik, Indrani,Banik, Bimal Krishna
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p. 1385 - 1387
(2020/06/27)
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- Magnetic core-shell Fe3O4@C-SO3H as an efficient and renewable 'Green catalyst' for the synthesis of O-2,3-unsaturated Glycopyra-nosides
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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.
- Sun, Guosheng,Qiu, Saifeng,Ding, Zekun,Chen, Heshan,Zhou, Jiafen,Wang, Zhongfu,Zhang, Jianbo
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supporting information
p. 347 - 352
(2017/02/10)
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- Structure-based design, synthesis and antitumoral evaluation of enulosides
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Enulosides, carbohydrate derivatives containing an α,β-unsaturated carbonyl unit, were designed and obtained in high yields and isomeric purity. All synthesized compounds exhibited antitumoral activity in micromolar range against four tested tumor cells lines, being the best results observed for HL-60?cells. These compounds open new possibilities to prepare an array of more active, site-specific or selective antitumor agents. 2016 Elsevier Ltd. All rights reserved.
- Santos, Jonh A.M.,Santos, Cosme S.,Almeida, Claudia L.A.,Silva, Thiago D.S.,Freitas Filho, Jo?o R.,Milit?o, Gardenia C.G.,da Silva, Teresinha G.,da Cruz, Carlos H.B.,Freitas, Juliano C.R.,Menezes, Paulo H.
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p. 192 - 201
(2017/02/15)
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- Stereoselective synthesis of D-galactal-derived N-ethoxycarbonyl aziridine, as a new, improved synthetic protocol to glycal-derived N-activated vinyl aziridines
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A new protocol for the synthesis of D-galactal-derived N-ethoxycarbonyl vinyl aziridine 1β-CO2Et, starting from tri-O-acetyl-D-glucal, is described. The new protocol constitutes a simple and fast access, with a satisfactory overall yield (5 steps, 36%), to a D-galactal-derived vinyl aziridine with a clear improvement compared with the previously described procedure leading to the structurally related N-nosyl aziridine 1β-Ns which, starting from the same precursor, proceeded through 13 steps with a low, decidedly unsatisfactory, overall yield (3%).
- Princiotto, Salvatore,Di Bussolo, Valeria,Bordoni, Vittorio,Favero, Lucilla,Crotti, Stefano,Uccello Barretta, Gloria,Balzano, Federica,Crotti, Paolo
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p. 829 - 837
(2017/01/25)
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- Gd(OTf)3 catalyzed preparation of 2,3-unsaturated O-, S-, N-, and C-pyranosides from glycals by Ferrier Rearrangement
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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.
- Chen, Peiran,Su, Jie
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supporting information
p. 84 - 94
(2015/12/23)
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- Hafnium(IV) triflate as a highly efficient catalyst for Ferrier rearrangement of O- and S-nucleophiles with glycals
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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.
- Liu, Yonghui,Song, Tianbang,Meng, Weijia,Xu, Yun,Wang, Peng George,Zhao, Wei
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supporting information
p. 2758 - 2762
(2016/06/09)
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- An efficient procedure for the synthesis of 2,3-unsaturated-O-glycosides: TiCl3(OTf) as the catalyst for type i Ferrier rearrangement
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An efficient type I Ferrier rearrangement reaction system for the synthesis of 2,3-unsaturated-O-glycosides has been established by using TiCl 3(OTf) as the catalyst. A series of 2,3-unsaturated-O-glucosides were prepared from 3,4,6-tri-O-acetyl-d-glucal in good yield and high anomeric selectivity.
- Chen, Peiran,Lin, Lei
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p. 4524 - 4531
(2013/06/27)
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- CF3SO3H-SiO2 as catalyst for Ferrier rearrangement: An efficient procedure for the synthesis of pseudoglycosides
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An efficient method for the conversion of 2,4,6-tri-O-acetyl-D-glucal to 2,3-unsaturated glycosides by using triflic acid on SiO2 as catalyst has been established. A series of 2,3-unsaturated glucosides were synthesized in good yield and high anomeric selectivity under transition metal-free conditions.
- Chen, Peiran,Wang, Shaoshan
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supporting information
p. 583 - 588
(2013/07/25)
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- RuCl3·3H2O as catalyst for Ferrier rearrangement: An efficient procedure for the preparation of pseudoglycosides
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By using RuCl3·3H2O as catalyst, an improved method for the synthesis of 2,3-unsaturated-glycosides has been established. A series of 2, 3-unsaturated-glucosides were obtained from 2,4,6-tri-O-acetyl-d- glucal or 3,4-di-O-acetyl-6-deoxy-l-glucal in good yield and high anomeric selectivity.
- Chen, Peiran,Lin, Lei
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supporting information
p. 10045 - 10051
(2013/11/06)
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- Stereoselective synthesis of pseudoglycosides catalyzed by TeCl4 under mild conditions
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Catalytic amounts of tellurium(IV) tetrachloride were used to promote the O-glycosylation of 3,4,6-tri-O-acetyl-d-glucal to give the corresponding 2,3-unsaturated-O-glycosides. With simple alcohols, the desired compounds were obtained in good yields and excellent anomeric selectivity in a short reaction time using only 2 mol % of the catalyst. The application of the method in the synthesis of a small set of glycopyranosides with rigid or flexible linkers gave the corresponding α anomers as products in good yields. Further applications of some of the synthesized compounds in allylation reaction of aldehydes gave the corresponding homoallylic alcohols in good yields.
- Freitas, Juliano C. R.,Couto, Tulio R.,Paulino, Antonio A. S.,Malvestiti, Ivani,Oliveira, Roberta A.,Menezes, Paulo H.,De Freitas Filho, Joao R.
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p. 10611 - 10620,10
(2012/12/12)
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- Stereoselective synthesis of pseudoglycosides catalyzed by TeCl4 under mild conditions
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Catalytic amounts of tellurium(IV) tetrachloride were used to promote the O-glycosylation of 3,4,6-tri-O-acetyl-d-glucal to give the corresponding 2,3-unsaturated-O-glycosides. With simple alcohols, the desired compounds were obtained in good yields and excellent anomeric selectivity in a short reaction time using only 2 mol % of the catalyst. The application of the method in the synthesis of a small set of glycopyranosides with rigid or flexible linkers gave the corresponding α anomers as products in good yields. Further applications of some of the synthesized compounds in allylation reaction of aldehydes gave the corresponding homoallylic alcohols in good yields.
- Freitas, Juliano C.R.,Couto, Túlio R.,Paulino, Ant?nio A.S.,De Freitas Filho, Jo?o R.,Malvestiti, Ivani,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 8645 - 8654
(2012/10/29)
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- Iron(III) triflate, a new efficient catalyst for Type i Ferrier Rearrangement
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By using iron(III) triflate as catalyst, an improved method for the synthesis of 2,3-unsaturated-O-glycosides has been established. A series of 2,3-unsaturated-O-glucosides were obtained from 2,4,6-tri-O-acetyl-d-glucal in good yield and high anomeric selectivity.
- Chen, Peiran,Wang, Shaoshan
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supporting information; experimental part
p. 5356 - 5362
(2012/09/07)
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- Efficient pseudo-enantiomeric carbohydrate olefin ligands
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Highly efficient pseudo-enantiomeric olefin ligands were designed from d-glucose and d-galactose. These ligands yield consistently excellent levels of enantioselectivity in Rh(I)-catalyzed 1,4-additions of aryl- and alkenylboronic acids to achiral enones and high diastereoselectivity with chiral substrates. Contrary to established olefin ligands, they are obtained enantiomerically pure via short syntheses without racemic resolution steps, making them a valuable addition to the arsenal of chiral ligands with olefinic donor sites.
- Grugel, Holger,Albrecht, Fabian,Minuth, Tobias,Boysen, Mike M. K.
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supporting information; experimental part
p. 3780 - 3783
(2012/09/08)
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- Amine-linked diglycosides: Synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays
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Diglycose derivatives, consisting of two monosaccharides linked at non-anomeric positions by a bridging nitrogen atom, have been synthesised. Conversion of one of the precursor monosaccharide coupling components into an unsaturated derivative enhances its
- Cumpstey, Ian,Frigell, Jens,Pershagen, Elias,Akhtar, Tashfeen,Moreno-Clavijo, Elena,Robina, Inmaculada,Alonzi, Dominic S.,Butters, Terry D.
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supporting information; experimental part
p. 1115 - 1123
(2011/10/08)
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- A facile H2SO4/4 ? molecular sieves catalyzed synthesis of 2,3-unsaturated O -glycosides via ferrier-type rearrangement
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A novel method for synthesizing 2,3-unsaturated glycosides has been developed using a metal-free catalytic system. This catalyst, sulfuric acid/4 molecular sieves can catalyze the reaction of 3,4,6-tri-O-acetyl-d-glucals and a wide range of alcohols at room temperature, affording 2,3-unsaturated glycosides in good -selectivity (α/β> 6:1) via a Ferrier-type rearrangement. Georg Thieme Verlag Stuttgart - New York.
- Zhou, Jiafen,Zhang, Bo,Yang, Guofang,Chen, Xuan,Wang, Qingbing,Wang, Zhongfu,Zhang, Jianbo,Tang, Jie
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experimental part
p. 893 - 896
(2010/07/16)
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- H2SO4-SiO2: Highly efficient and novel catalyst for the Ferrier-type glycosylation
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Sulfuric acid immobilized on silica gel is designed as a very useful catalyst for synthesis of 2,3-unsaturated glycopyranosides. This handy, metal-free, environment friendly transformation provides high yields and α-stereoselectivities in a very few amount (0.02 eq.) of catalyst and in short reaction times (10 min).
- Zhou, Jia Fen,Chen, Xuan,Wang, Qing Bing,Zhang, Bo,Zhang, Li Yan,Yusulf, Abdullh,Wang, Zhong Fu,Zhang, Jian Bo,Tang, Jie
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experimental part
p. 922 - 926
(2011/11/12)
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- Kinetically controlled Ferrier rearrangement of 3-O-mesyl-d-glycal derivatives
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The Ferrier rearrangement, which is widely used in carbohydrate chemistry, is generally performed under acidic conditions to give an α anomer with high stereoselectivity. We have found that 3-O-mesyl-d-glycals 2-4 were smoothly reacted with alcohols in th
- Watanabe, Yuhya,Itoh, Tsubasa,Sakakibara, Tohru
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scheme or table
p. 516 - 520
(2009/05/11)
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- Microwave-enhanced Ferrier reaction: A facile synthesis of 2,3-unsaturated-O-glycosides under solvent-free conditions
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A variety of 2,3-unsaturated- O -glycosides have been prepared by the Ferrier rearrangement of acetyl protected glycals under microwave irradiation using silica gel as an acid catalyst. Environmental friendliness, high yields, and short reaction times are the key features of this method. Furthermore, the method was applicable not only to the Ferrier reaction of 3,4,6-tri- O -acetyl glucal and 3,4,6-tri- O -acetyl galactal but also to the Ferrier reaction of 3,4-di- O -acetyl arabinal. Copyright Taylor & Francis Group, LLC.
- Du, Wenting,Hu, Yongzhou
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p. 2035 - 2046
(2007/10/03)
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- Ferrier rearrangement catalyzed by HClO4-SiO2: Synthesis of 2,3-unsaturated glycopyranosides
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Alkyl 2,3-unsaturated glycopyranosides have been prepared by the Ferrier rearrangement of acetyl protected glycals catalyzed by HClO4-SiO 2. Operational simplicity, use of economically convenient catalyst, mild reaction conditions, high yields, short reaction times are the key features of this protocol.
- Misra, Anup Kumar,Tiwari, Pallavi,Agnihotri, Geetanjali
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p. 260 - 266
(2007/10/03)
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- TRANSACETALISATION PROCESS
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The invention relates to the resolution of racemic mixtures, and in particular to the separation of enantiomers of chiral alcohols utilising recyclable chiral auxiliaries. The present invention also relates to a process for preparing these recyclable chiral auxiliaries using an enantiomerically pure alcohol.
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Page/Page column 43-44
(2010/02/13)
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- Microwave-induced, Montmorillonite K10-catalyzed Ferrier rearrangement of tri-O-acetyl-D-galactal: Mild, eco-friendly, rapid glycosidation with allylic rearrangement
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Montmorillonite K10 was found to catalyze, under microwave irradiation, rapid O-glycosidation of 3,4,6-tri-O-acetyl-D-galactal to afford exclusively the alkyl and aryl 2,3-dideoxy-D-threo-hex-2-enopyranosides with very high α-selectivity and without the formation of the 2-deoxy-D-lyxo-hexopyranosides. Under these conditions, 3,4,6-tri-O-acetyl-D-glucal as usual also underwent the Ferrier rearrangement.
- Shanmugasundaram, Bhagavathy,Bose, Ajay K.,Balasubramanian, Kalpattu K.
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p. 6795 - 6798
(2007/10/03)
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- Highly stereoselective synthesis of pseudoglycals via Yb(OTf)3 catalyzed Ferrier glycosylation
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The reaction of tri-O-acetyl-D-glucal with various alcohols and thiols was effectively promoted by a catalytic amount of Yb(OTf)3 to produce a variety of pseudoglycals via Ferrier rearrangement in excellent yields and anomeric selectivity.
- Takhi,Abdel-Rahman,Schmidt
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p. 427 - 429
(2007/10/03)
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- Scandium triflate catalyzed ferrier rearrangement: An efficient synthesis of 2,3-unsaturated glycopyranosides
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Scandium(III) trifluoromethanesulfonate is found to catalyze efficiently the O-glycosidation of 3,4,6-tri-O-acetyl-D-glucal with various alcohols and phenols to afford the corresponding 2,3-unsaturated glycosides in excellent yields with good anomeric selectivity.
- Yadav,Reddy,Murthy,Kumar
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p. 1450 - 1451
(2007/10/03)
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- The preparation of amino sugars and branched-chain sugars by palladium-catalyzed allylic substitution of alkyl hex-2-enopyranosides
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Ethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (1) in the presence of triphenylphosphine and a catalytic amount of tetrakis(triphenylphosphine)palladium(0) reacted with a variety of amines or with reactive methylene compounds to give high yields of products aminated or C-alkylated, respectively, in allylic position.Some analogous experiments were performed using the β-D-erythro anomer (2) and the α-D-threo epimer (3) of 1.The constitutions and configurations of the new products were established by means of mass spectra, 13C- and 1H-nmr spectra, and optical rotation data.The reactions of 1 were found to be highly regio- and stereoselective, giving almost exclusively 4-substituted 2-enopyranosides with retention of configuration, except in the case of dibenzylamine which produced a mixture of the corresponding enoside and its 2-substituted, 3,4-unsaturated isomer ahving the α-D-threo configuration.The reactions of 2 appeared slightly less selective although they, too, furnished mainly 4-substituted 2-enopyranosides with retention of configuration.Regioselectivity was low or lacking in two C-alkylations performed with 3, which gave mixtures of 4-substituted 2-enosides and 2-substituted 3-enosides.Some aspects of conformation and optical rotation in enopyranosides are discussed.
- Baer, Hans H.,Hanna, Zaher S.
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p. 889 - 906
(2007/10/02)
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