86049-38-9Relevant academic research and scientific papers
Palladium-Catalyzed Cross-Coupling of Furfuryl Alcohols with Arylboronic Acids via Aromatization-Driven Carbon?Carbon Bond Cleavage to Synthesize 5-Arylfurfuryl Alcohols and 2,5-Diaryl Furans
Huang, Guanghao,Yin, Biaolin
supporting information, p. 5576 - 5586 (2019/11/14)
Herein we report a protocol for novel palladium-catalyzed cross-coupling reactions of sustainably produced primary furfuryl alcohols with arylboronic acids to deliver 5-arylfurfuryl alcohols and 2,5-diaryl furans. Hammett plot analysis suggested that the reaction mechanism involved aromatization-driven cleavage of the carbon?carbon bond of a furan oxonium ion intermediate. This protocol provides a simple, practical way to transform 5-hydroxymethylfurfural into useful compounds. (Figure presented.).
Palladium-catalyzed C-H formylation of electron-rich heteroarenes through radical dichloromethylation
Bao, Yan,Wang, Jian-Yong,Zhang, Ya-Xuan,Li, Yan,Wang, Xi-Sheng
, p. 3147 - 3150 (2018/07/13)
A novel palladium-catalyzed C-H formylation of electron-rich N-, O-, and S-containing heteroarenes has been developed. The key to success is that the commercially available BrCHCl2 was used as a stoichiometric carbonyl source. Mechanistic investigations indicated that different from the known Reimer-Tiemann reaction, this net C-H formylation proceeded through an electrophilc radical-type path.
Murai Reaction on Furfural Derivatives Enabled by Removable N,N′-Bidentate Directing Groups
Pezzetta, Cristofer,Veiros, Luis F.,Oble, Julie,Poli, Giovanni
supporting information, p. 8385 - 8389 (2017/06/28)
Furfural and related compounds are industrially relevant building blocks obtained from lignocellulosic biomass. To enhance the added value of these renewable resources, a Ru-catalyzed hydrofurylation of alkenes, involving a directed C?H activation at C3 of the furan ring, was developed. A thorough experimental study revealed that a bidentate amino-imine directing group enabled the desired coupling. Removal of the directing group occurred during the purification step, directly releasing the C3-functionalized furfurals. Development of the reaction as well as optimization and scope of the method were described. A mechanism was proposed on the basis of DFT calculations.
Synthesis of biologically active natural products, aspergillides A and B, entirely from biomass derived platform chemicals
Koh,Loh
supporting information, p. 3746 - 3750 (2015/07/15)
The depletion of finite fossil fuels drives the need to develop sustainable chemical feedstock such as biomass. The synthesis of biologically active natural products aspergillides A and B was achieved whereby all the carbon atoms present originated from biomass derived platform chemicals such as ethanol, levulinic acid and 5-hydroxymethylfurfural (HMF). The key steps in this synthesis include Noyori's asymmetric transfer hydrogenation, Achmatowicz rearrangement coupled with a triple reduction sequence, micellar Negishi coupling as well as an enzymatic kinetic resolution. Lipshutz's micellar Negishi coupling was also successfully applied on an advanced synthetic intermediate for the first time with good yield and excellent selectivity. This synthesis demonstrates the feasibility of constructing biologically active compounds using a sustainable chemical feedstock like biomass.
Trienamines derived from 5-substituted furfurals: Remote ε-functionalization of 2,4-dienals
Coelho, Jaime A. S.,Trindade, Alexandre F.,Andr, Vnia,Teresa Duarte,Veiros, Luis F.,Afonso, Carlos A.M.
, p. 9324 - 9328 (2014/12/11)
The selective ε-functionalization of 5-substituted furfurals via trienamine intermediates is reported herein. This methodology was successfully applied to several 5-substituted furfurals with different amines via formation of a trienamine through the furan ring. The rationalized reaction mechanism involves the addition of the trienamine intermediate to its corresponding iminium-ion producing new furan-containing scaffolds.
Metal-free trifluoromethylation of aromatic and heteroaromatic aldehydes and ketones
Qiao, Yupu,Si, Tuda,Yang, Ming-Hsiu,Altman, Ryan A.
, p. 7122 - 7131 (2014/08/18)
The ability to convert simple and common substrates into fluoroalkyl derivatives under mild conditions remains an important goal for medicinal and agricultural chemists. One representative example of a desirable transformation involves the conversion of aromatic and heteroaromatic ketones and aldehydes into aryl and heteroaryl β,β,β-trifluoroethylarenes and -heteroarenes. The traditional approach for this net transformation involves stoichiometric metals and/or multistep reaction sequences that consume excessive time, material, and labor resources while providing low yields of products. To complement these traditional strategies, we report a one-pot metal-free decarboxylative procedure for accessing β,β,β- trifluoroethylarenes and -heteroarenes from readily available ketones and aldehydes. This method features several benefits, including ease of operation, readily available reagents, mild reaction conditions, high functional-group compatibility, and scalability.
Chemistry of glucal halohydrins(II): An unusual protecting group effect in the competitive formation of formyl furanosides and methyl glycosides
Kozlowski, John S.,Marzabadi, Cecilia H.,Rath, Nigam P.,Spilling, Christopher D.
, p. 301 - 313 (2007/10/03)
A remarkable protecting group influence was observed in the base-induced reaction of protected halohydrins derived from D-glycals. Tri-O-methyl and tri-O-benzyl halohydrins react with cesium carbonate in methanol at room temperature to give methyl glycosides as the major product and unsaturated formyl furanosides as the minor product. Whereas, the tri-O-tert-butyldimethylsilyl (t-BuMe2Si)-protected halohydrins reacted with cesium carbonate in methanol at room temperature to give a mixture of epimeric formyl furanosides, and at reflux to give an unsaturated formyl furanoside, as the only products. The tri-O-methyl and tri-O-benzyl halohydrins react slowly at elevated temperature to give predominantly furans. In comparison, the tri-O-t-BuMe2Si halohydrins reacted completely after five minutes to give a mixture of epimeric formyl furanosides. The tri-O-t-BuMe2Si iodohydrins were oxidized to the corresponding iodolactones, which also underwent a based-induced ring contraction in methanol to give the furanose 1-methylcarboxylate esters.
Convenient syntheses of 2,3,4,6-tetra-O-alkylated D-glucose and D-galactose
Kaesbeck, Ludwig,Kessler, Horst
, p. 169 - 173 (2007/10/03)
Convenient syntheses of the 2,3,4,6-tetra-O-benzylated and -allylated D-glucopyranoses 1 and 2 and the corresponding D-galactopyranoses 3 and 4 are described. The D-glucose derivatives 1 and 2 were obtained from inexpensive sucrose by peralkylation and subsequent acid hydrolysis. In this reaction sequence an alkylated D-fructofuranosyl cation is generated which was trapped by different nucleophiles to afford 4-benzyloxymethylenefurfural (8) and the alkylated D-fructosides 7, 8 and 10. On the other hand 2,3,4,6-tetra-O-benzyl-D-galactose 3 was synthesized by oxidative cleavage of ethyl 2,3,4,6-tetra-O-benzyl-1-thio-α,β-D-galactopyranoside (11) with aqueous N-bromosuccinimide. The alternative route for the preparation of 2,3,4,6-tetra-O-allyl-D-glucopyranoside (2) via p-methoxybenzyl β-D-glucoside is less attractive. However, this route was used for the synthesis of 2,3,4,6-tetra-O-allyl-D-galactose (4). VCH Verlagsgesellschaft mbH, 1997.
Syntheses of γ-oxo acids or γ-oxo esters by photooxygenation of furanic compounds and reduction under ultrasound: Application to the synthesis of 5-aminolevulinic acid hydrochloride
Cottier,Descotes,Eymard,Rapp
, p. 303 - 306 (2007/10/02)
The photooxygenation of 5-hydroxymethyl-2-furfural (1a) or derivatives 1b-g yields 4-hydroxy-Δ2-butenolides 2 which are the percursors of butenolides 3 or α,β-unsaturated γ-oxo esters 5. The selective reduction of olides 2 or oxo esters 5 with zinc in acetic acid under sonication leads to γ-oxo acids 4 or γ-oxo esters 6. The photooxygenation of amino derivative 1d, followed by selective reduction of corresponding lactone 2d, gives 5-aminolevulinic acid hydrochloride (7) (ALA) after hydrolysis.
Stereocontrolled Synthesis of Spirodihydrouracil Nucleoside
Sano, Hiromi,Mio, Shigeru,Kitagawa, Junko,Sugai, Soji
, p. 2233 - 2240 (2007/10/02)
Synthesis of the spiro-dihydrouracil derivative of (+)-hydantocidin (2) is described.The pivotal step is a Lewis acid-mediated C-glycosidation of the protected D-psicose 3 with trimethylsilyl cyanide, which proceeded in good yield and β-selectivity.Synthe
