- Synthesis of [2,2’]Bifuranyl-5,5’-dicarboxylic Acid Esters via Reductive Homocoupling of 5-Bromofuran-2-carboxylates Using Alcohols as Reductants?
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Herein, we describe an environmentally benign and cost-effective protocol for the synthesis of valuable bifuranyl dicarboxylates, starting with α-bromination of readily accessible furan-2-carboxylates by LiBr and K2S2O8. Furthermore, the bromination intermediate product 5-bromofuran-2-carboxylates were then conducted in a palladium-catalyzed reductive homocoupling reactions in the presence of alcohols to afford bifuranyl dicarboxylates. One of the final products in this protocol, [2,2’]bifuran-5,5’-dicarboxylic acid esters, are essential monomers of poly(ethylene bifuranoate), which can be served as an green and versatile alternative polymer for traditional poly(ethylene terephthalate) that is currently common in technical plastics.
- Jiang, Huanfeng,Luo, Jiajun,Xie, Yi,Yin, Biaolin,Yu, Bin
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- A CO2-Catalyzed Transamidation Reaction
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Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular,N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2
- Yang, Yang,Liu, Jian,Kamounah, Fadhil S.,Ciancaleoni, Gianluca,Lee, Ji-Woong
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p. 16867 - 16881
(2021/11/18)
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- Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones
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We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η3-bound Ni(II) enolate as the key selectivity-controlling intermediate.
- Guven, Sinem,Kundu, Gourab,Rissanen, Kari,Schoenebeck, Franziska,Ward, Jas S.,We?els, Andrea
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supporting information
p. 8375 - 8380
(2021/06/27)
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- Br?nsted Base-Catalyzed Transformation of α,β-Epoxyketones Utilizing [1,2]-Phospha-Brook Rearrangement for the Synthesis of Allylic Alcohols Having a Tetrasubstituted Alkene Moiety
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A stereoselective transformation of α,β-epoxyketones into alkenylphosphates having a hydroxymethyl group on the β-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Br?nsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.
- Kondoh, Azusa,Tasato, Naoko,Aoki, Takuma,Terada, Masahiro
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supporting information
p. 5170 - 5175
(2020/07/04)
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- Simple Synthesis of Amides via Their Acid Chlorides in Aqueous TPGS-750-M
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The technology of surfactant chemistry is employed for amide bond construction via the reaction of acyl chlorides with amines in 2 wt % TPGS-750-M aqueous solution. Specifically, this highly efficient method enables a chromatography-free scalable process and recycling of the TPGS-750-M solution.
- Shi, Min,Ye, Ning,Chen, Wei,Wang, Hui,Cheung, Chiming,Parmentier, Michael,Gallou, Fabrice,Wu, Bin
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supporting information
p. 1543 - 1548
(2020/11/23)
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- Direct Alkoxycarbonylation of Heteroarenes via Cu-Mediated Trichloromethylation and in Situ Alcoholysis
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We report an efficient approach for direct alkoxycarbonylation of furans as well as other heteroarenes via a one-step copper-mediated reaction of three components (i.e., heteroarene, alcohol, and CHCl3). The copper additive was confirmed to simultaneously promote the reaction in three pathways: oxidant cracking, single electron transfer, and alcoholysis. By means of this protocol, various functionalized furancarboxylates and other heteroarenecarboxylates were facilely obtained in moderate to good yields.
- Jiang, Huanfeng,Jiang, Kai,Li, Yingwei,Luo, Wenkun,Yin, Biaolin
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supporting information
(2020/03/04)
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- Iron-Catalyzed Oxidative Decarbonylative α-Alkylation of Acyl-Substituted Furans with Aliphatic Aldehydes as the Alkylating Agents
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A protocol for FeCl2-catalyzed oxidative decarbonylative α-alkylation of acyl furans using alkyl aldehydes as the alkylating agents has been developed. This protocol affords α-alkyl-α-acylfurans in moderate to good yields in a practical and sustainable fa
- Luo, Wenkun,Yang, Yongjie,Liu, Bo,Yin, Biaolin
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p. 9396 - 9404
(2020/08/14)
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- Saturated Bioisosteres of ortho-Substituted Benzenes
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Saturated bioisosteres of ortho-disubstituted benzenes (bicyclo[2.1.1]hexanes) were synthesized, characterized and validated. These cores were incorporated into the bioactive compounds Valsartan, Boskalid and Fluxapyroxad instead of the benzene ring. The
- Denisenko, Aleksandr,Garbuz, Pavel,Mykhailiuk, Pavel K.,Shishkina, Svetlana V.,Voloshchuk, Nataliya M.
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supporting information
p. 20515 - 20521
(2020/08/21)
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- Palladium-Catalyzed Hydrocarbonylative Cyclization of 1,5-Dienes
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A novel and atom-economic palladium-catalyzed isomerization-hydrocarbonylative cyclization reaction of 1,5-dienes to 2-alkylidenecyclopentanones has been developed, which provides a rapid and straightforward approach to 2-alkylidenecyclopentanones with high stereoselectivity. The reaction was found to proceed via alkene isomerization and selective hydrocarbonylative cyclization to generate 2-alkylidenecyclopentanones with high selectivity.
- Zou, Suchen,Gao, Bao,Huang, Yao,Zhang, Tianze,Huang, Hanmin
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supporting information
p. 6333 - 6336
(2019/08/26)
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- One-pot synthesis of Weinreb amides employing 3,3-dichloro-1,2-diphenylcyclopropene (CPI-Cl) as a chlorinating agent
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The synthesis of Nα-protected amino alkyl Weinreb amides starting from the corresponding α-amino acids as well as carboxylic acids has been delineated through the in situ generation of acid chlorides using CPI-Cl as a chlorinating agent. The protocol is simple; the reaction conditions employed were mild, and compatible with all the three commonly used urethane protecting groups namely, Boc, Cbz and Fmoc groups. The resulting Weinreb amides are obtained in good yields as optically pure products.
- Shekharappa,Roopesh Kumar,Sureshbabu, Vommina V.
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supporting information
p. 790 - 798
(2019/03/26)
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- A biosynthesis-inspired approach to over twenty diverse natural product-like scaffolds
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A synthetic approach to diverse scaffolds was developed that was inspired by diterpene biosynthesis. Initial scaffolds, generated using Diels-Alder reactions of furyl-functionalised amines, were transformed into alternative scaffolds using cleavage, ring expansion, annulation and rearrangement reactions. In total, 25 diverse scaffolds were prepared that were shown to have high natural product-likeness.
- Firth, James D.,Craven, Philip G. E.,Lilburn, Matthew,Pahl, Axel,Marsden, Stephen P.,Nelson, Adam
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supporting information
p. 9837 - 9840
(2016/08/04)
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- A new strategy for accessing (S)-1-(furan-2-yl)pent-4-en-1-ol: a key precursor of Ipomoeassin family of compounds and C1–C15 domain of halichondrins
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A highly efficient synthesis of (S)-1-(furan-2-yl)pent-4-en-1-ol, known to be an initial precursor of Ipomoeassin family of compounds and C1–C15 domain of halichondrins has been achieved via a sequence involving the use of Weinreb amide formation followed by Weinreb ketone synthesis and finally CBS (Corey–Bakshi–Shibata) reduction. Detailed study on improvement of each step is described. The title compound was converted to a potential cytotoxic agent for further pharmacological studies.
- Jammula, Subba Rao,Anna, Venkateswara Rao,Tatina, Sudhakar,Krishna, Thalishetti,Sreenivas, B. Yogi,Pal, Manojit
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supporting information
p. 3924 - 3928
(2016/08/09)
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- Reductive N-O cleavage of Weinreb amides by sodium in alumina and silica gels: synthetic and mechanistic studies
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The use of sodium in alumina and silica gels for the reductive cleavage of the N-O bond of N-methoxy-N-methylamides, commonly referred to as Weinreb amides, has been investigated. This method reduces a diverse set of Weinreb amides with different function
- Jackson, James E.,O'Brien, Brittany N.,Kedzior, Sonya K.,Fryz, Gage R.,Jalloh, Fatmata S.,Banisafar, Arash,Caldwell, Michael A.,Braun, Max B.,Dunyak, Bryan M.,Dye, James L.
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supporting information
p. 6227 - 6230
(2015/10/20)
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- Synthesis and antibacterial activities of cadiolides A, B and C and analogues
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The one-pot multicomponent synthesis of natural butenolides named cadiolides A, B, C and analogues has been realized. The antibacterial structure activity relationship shows that the presence of phenolic hydroxyl groups and the number and position of bromine atoms on the different aromatic rings are important features for antibacterial activity, besides it was demonstrated the tolerance of both benzene and furan ring at position 3 of the butenolide nucleus. Furthermore, none of the most relevant antibacterial compounds showed any cytotoxicity in freshly isolated human neutrophils.
- Boulangé, Agathe,Parraga, Javier,Galán, Abraham,Cabedo, Nuria,Leleu, Stéphane,Sanz, Maria Jesus,Cortes, Diego,Franck, Xavier
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p. 3618 - 3628
(2015/07/27)
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- Visible-Light-Mediated Generation of Nitrogen-Centered Radicals: Metal-Free Hydroimination and Iminohydroxylation Cyclization Reactions
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The formation and use of iminyl radicals in novel and divergent hydroimination and iminohydroxylation cyclization reactions has been accomplished through the design of a new class of reactive O-aryl oximes. Owing to their low reduction potentials, the inexpensive organic dye eosin Y could be used as the photocatalyst of the organocatalytic hydroimination reaction. Furthermore, reaction conditions for a unique iminohydroxylation were identified; visible-light-mediated electron transfer from novel electron donor-acceptor complexes of the oximes and Et3N was proposed as a key step of this process.
- Davies, Jacob,Booth, Samuel G.,Essafi, Stephanie,Dryfe, Robert A. W.,Leonori, Daniele
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supporting information
p. 14017 - 14021
(2016/01/25)
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- One-pot transition-metal-free synthesis of weinreb amides directly from carboxylic acids
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Weinreb amides were prepared directly from carboxylic acids, N,O-dimethylhydroxylamine, and phosphorus trichloride in one pot at 60 °C in toluene in high yields, thus avoiding the separation of the moisture and air sensitive intermediate P[NMe(OMe)]3 in advance. Sterically hindered carboxylic acids also give the corresponding Weinreb amides in excellent yields. Various functional groups are tolerated on the carboxylic acid. The method, which is a simple process and gives high yields, is suitable for large-scale production. Georg Thieme Verlag KG Stuttgart · New York.
- Niu, Teng,Wang, Ke-Hu,Huang, Danfeng,Xu, Changming,Su, Yingpeng,Hu, Yulai,Fu, Ying
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p. 320 - 330
(2014/02/14)
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- Synthesis of functionalised 4H-quinolizin-4-ones via tandem Horner-Wadsworth-Emmons olefination/cyclisation
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4H-Quinolizin-4-ones are a unique class of heterocycle with valuable physicochemical properties and which are emerging as key pharmacophores for a range of biological targets. A tandem Horner-Wadsworth-Emmons olefination/cyclisation method has been developed to allow facile access to substituted 4H-quinolizin-4-ones encoded with a range of functional groups.
- Muir, Calum W.,Kennedy, Alan R.,Redmond, Joanna M.,Watson, Allan J. B.
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supporting information
p. 3337 - 3340
(2013/06/05)
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- Highly efficient and environmentally benign preparation of Weinreb amides in the biphasic system 2-MeTHF/water
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A straightforward chromatography-free preparation of Weinreb amides starting from acid halides has been achieved in the biphasic medium 2-MeTHF/water. Analytically pure compounds were isolated in excellent yields simply after removal of 2-MeTHF, which abs
- Pace, Vittorio,Castoldi, Laura,Alcantara, Andres R.,Holzer, Wolfgang
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p. 10158 - 10162
(2013/09/02)
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- Versatile synthesis of acylfuranones by reaction of acylketenes with α-hydroxy ketones: Application to the one-step multicomponent synthesis of cadiolide B and its analogues
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Functionalized acylfuranones have been prepared in a one-step procedure by thermal fragmentation of the corresponding dioxinones in the presence of hydroxy ketones in basic conditions. Multicomponent reactions also occur on addition of an aldehyde as a third reaction partner resulting in an expeditious access to cadiolide B and its analogues. A new method for the synthesis of acylfuranones is described based on the fragmentation of dioxinones to acylketenes followed by trapping with hydroxy ketones. Addition of an aldehyde as a third reaction partner leads to a supplementary aldolization/crotonization sequence resulting in an expeditious synthesis of cadiolide B and its analogues. Copyright
- Peixoto, Philippe Alexandre,Boulange, Agathe,Leleu, Stephane,Franck, Xavier
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p. 3316 - 3327
(2013/06/27)
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- Ru-catalyzed hydrogenation of 3,5-diketo amides: Simultaneous control of chemo- and enantioselectivity
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By modulating the chelating priorities of the different directing groups in 3,5-diketo amides with the assistance from coordinating solvent, highly chemo- and enantioselective hydrogenation of the C3-carbonyls was achieved in the presence of [RuCl(benzene)(S)-SunPhos]Cl in THF.
- Li, Wanfang,Fan, Weizheng,Ma, Xin,Tao, Xiaoming,Li, Xiaoming,Xie, Xiaomin,Zhang, Zhaoguo
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supporting information
p. 8976 - 8978
(2012/11/07)
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- Arylation of 2-furyl 4-fluorophenyl ketone: An extension of heck chemistry towards novel integrase inhibitors
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An optimized procedure for the direct and regioselective arylation of 2-acylfurans has been developed. The versatility of this protocol has been evaluated on a series of aryl and heteroaryl halides, thus obtaining a small collection of 2,5-disubstituted f
- Franchi, Luigi,Rinaldi, Marta,Vignaroli, Giulia,Innitzer, Anna,Radi, Marco,Botta, Maurizio
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experimental part
p. 3927 - 3933
(2010/12/29)
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- A powerful reagent for synthesis of weinreb amides directly from carboxylic acids
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A powerful reagent, P[NCH3(OCH3)]3 (3), for conversion of carboxylic acids directly to Weinreb amides was developed. In most cases the yields of the corresponding Weinreb amides were above 90% when P[NCH3(OCHsu
- Niu, Teng,Zhang, Weiming,Huang, Danfeng,Xu, Changming,Wang, Haifeng,Hu, Yulai
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scheme or table
p. 4474 - 4477
(2009/12/24)
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- Aluminum-catalyzed asymmetric alkylations of pyridyl-substituted alkynyl ketones with dialkylzinc reagents
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Alkylations of pyridyl-substituted ynones with Et2Zn and Me 2Zn, promoted by amino acid-based chiral ligands in the presence of Al-based alkoxides, afford tertiary propargyl alcohols efficiently in 57% to >98% ee. Two easily accessib
- Friel, Donna K.,Snapper, Marc L.,Hoveyda, Amir H.
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supporting information; experimental part
p. 9942 - 9951
(2009/02/04)
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- Method of making 2-furylalkylketones
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A method of making a compound by: providing a furyl compound being 2-furoyl chloride or corresponding carboxylic acid, amide, ester, anhydride, or lactone; reacting the furyl compound with CH3O(CH3)NH.HCl to form an amide; reacting the amide with an alkane Grignard reagent or alkyllithium to form a chelated intermediate; and reacting the chelated intermediate with an aqueous acid to form a (2-furyl)-alkylketone.
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Page/Page column 4
(2010/11/25)
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- Stereoselective synthesis of substituted N-heterocycles via sequential cross metathesis-reductive cyclization
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A diastereoselective synthesis of substituted piperidine and pyrrolidine derivatives is presented, employing a highly selective cross metathesis (CM) reaction followed by a domino reduction-cyclization process. A diastereoselective synthesis of substituted mono- and bicyclic-piperidine and pyrrolidine derivatives is presented, employing a highly selective cross metathesis (CM) reaction followed by a domino reduction-cyclization process.
- Gebauer, Julian,Dewi, Purnama,Blechert, Siegfried
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- A mild, one-pot method for the conversion of carboxylic acids into the corresponding Weinreb amides
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Reaction of various carboxylic acids with N,O-dimethylhydroxylamine under modified Mukaiyama amide coupling conditions affords the corresponding Weinerb amides in generally high yield.
- Banwell,Smith
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p. 2011 - 2019
(2007/10/03)
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- A ROMPGEL-supported N-hydroxysuccinimide: A host of acylations with minimal purification
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(formula presented) amides, carbamates, ureas, Weinreb amides, hydroxamic acids Yields 89-98% Purity > 95% A novel N-hydroxysuccinimide ring-opening metathesis polymer is described as a recyclable supported acyl transfer reagent. Amides, carbamates, ureas, Weinreb amides, and hydroxamic acids are all obtained in excellent yields and purities from amines with minimal purification.
- Barrett, Anthony G. M.,Cramp, Susan M.,Roberts, Richard S.,Zecri, Frederic J.
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p. 261 - 264
(2007/10/03)
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- Efficient method for preparation of N-methoxy-N-methyl amides by reaction of lactones or esters with Me2AlCl-MeONHMe·HCl
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The reaction of a lactone or an ester with dimethylaluminum chloride and N, O-dimethylhydroxylamine hydrochloride provided an efficient method for preparation of N-methoxy-N-methyl amide.
- Shimizu, Takeshi,Osako, Katsuhisa,Nakata, Tadashi
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p. 2685 - 2688
(2007/10/03)
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- The birch reduction of heterocyclic compounds. 11. Birch reduction and reductive alkylation of furamides
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The Birch reduction-alkylation of some N,N-dialkylfuramides and its application to the useful intermediates for the natural product synthesis are described.
- Kinoshita, Takamasa,Ichinari, Daisuke,Sinya, Junko
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p. 1313 - 1317
(2007/10/03)
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