149561-65-9

Upstream product

• 117249-17-9 3,4-di-O-benzyl-L-rhamnal 
• 101856-96-6 (2S,3S,4S)-4-(tert-butyldimethylsilyloxy)-3,4-dihydro-3-hydroxy-2-methyl-2H-pyran 
• 53657-42-4 L-rhamnal 
• 293736-30-8 3-O-(tert-butyldimethylsilyl)oxy-4-O-benzyl-L-rhamnal 
• 34819-86-8 3,4-di-O-acetyl-6-deoxy-L-glucal 
• 69980-52-5 2,3,4-tri-O-acetyl-L-rhamnopyranosyl bromide 
• 108-22-5 Isopropenyl acetate 
• 117249-16-8 1,5-anhydro-2,6-dideoxy-4-O-(phenylmethyl)-L-arabino-hex-1-enitol 

Downstream Products

• 106988-79-8 1,5-Anhydro-3,4-di-O-benzyl-2,6-didesoxy-L-ribo-hex-1-enit 
• 106988-70-9 1,5-Anhydro-4-O-benzyl-2,6-dideoxy-L-ribo-hex-1-enitol 

Relevant academic research and scientific papers

Palladium-Catalyzed Reaction of Aryl Iodides and Glycal Enones: Application in the Preparation of Dapagliflozin Analogues

An efficient approach for the preparation of C-1 aryl enones from aryl iodides and glycal enones by palladium-catalyzed cross-coupling reactions under ligand-free conditions was developed. A wide range of aryl iodides bearing electron-donating and withdrawing groups underwent oxidative C-1 arylation with galactal, glucal and rhamnal enones in the presence of Pd(OAc)2 and AgNO3 under mild conditions. The protecting groups, including benzyl, acetyl, pivaloyl, and benzoyl groups, were found to be compatible under standard reaction conditions. The developed methodology was applied for the preparation of dapagliflozin analogues (SGLT-2 inhibitors). Regioselective nitration of C-1 aryl enones provides C-2 nitro aryl enones in good yields.

Synthesis of the α-Linked Digitoxose Trisaccharide Fragment of Kijanimicin: An Unexpected Application of Glycosyl Sulfonates

Previously, we demonstrated that glycosyl tosylates are effective for the synthesis of β-glycosides of gluco-configured 2-deoxy sugars. Here, we show the same sulfonate system can be used for the selective synthesis of α-glycosides containing the allo-con

Automated, Multistep Continuous-Flow Synthesis of 2,6-Dideoxy and 3-Amino-2,3,6-trideoxy Monosaccharide Building Blocks

An automated continuous flow system capable of producing protected deoxy-sugar donors from commercial material is described. Four 2,6-dideoxy and two 3-amino-2,3,6-trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open-source Python-controlled automation platform.

Development of Routes for the Stereoselective Preparation of β-Aryl- C-glycosides via C-1 Aryl Enones

A wide range of enones derived from d-glucal, d-galactal, l-rhamnal, d-rhamnal, and l-arabinal underwent Heck-coupling with various arylboronic acids bearing electron-donating and -withdrawing groups in the presence of palladium acetate and 1,10-phenanthroline. These reactions provided synthetically useful C-1 aryl enones in good yields. Many sensitive functional groups as well as protecting groups present in arylboronic acids and enones, respectively, remained intact under optimized conditions. The stereoselective hydrogenation of C-1 aryl enones with Pd-C/H2 provides the β-isomer of 2-deoxy-aryl-C-glycosides in excellent yield. The C-1 aryl enones were also used as precursors for the synthesis of 2-hydroxy-β-aryl-C-glycosides. Regioselective C-2 halogenations and vinylations of C-1 aryl enones were achieved in excellent yields.

Rapid de Novo Preparation of 2,6-Dideoxy Sugar Libraries through Gold-Catalyzed Homopropargyl Orthoester Cyclization

A flexible de novo route capable of producing libraries of 2,6-dideoxy sugars is described. We have found that Au(JackiePhos)SbF6MeCN promotes the conversion of homopropargyl orthoesters into functionalized 2,3-dihydro-4H-pyran-4-ones in good t

Palladium-Catalyzed One-Pot Stereospecific Synthesis of 2-Deoxy Aryl C-Glycosides from Glycals and Anilines in the Presence of tert-Butyl Nitrite

The palladium-catalyzed one-pot synthesis of 2,3-deoxy-3-keto aryl C-glycosides is achieved from glycals and anilines in the presence of tert-butyl nitrite and aqueous HBF 4 under mild conditions. This one-pot method stereospecifically provides α-and β-Aryl glycosides (≥19:1 by NMR) in good yields at room temperature. The configuration at the C-3 position in the glycal determines the anomeric selectivity (i.e., α or β) of the desired products.

Epimerization of glycal derivatives by a cyclopentadienylruthenium catalyst: Application to metalloenzymatic DYKAT

Epimerization of a non-anomeric stereogenic center in carbohydrates is an important transformation in the synthesis of natural products. In this study an epimerization procedure of the allylic alcohols of glycals by cyclopentadienylruthenium catalyst 1 is presented. The epimerization of 4,6-O-benzylidene-d-glucal 4 in toluene is rapid, and an equlibrium with its d-allal epimer 5 is established within 5 min at room temperature. Exchange rates for allal and glucal formation were determined by 1D 1H EXSY NMR experiments to be 0.055 s-1 and 0.075 s -1, respectively. For 4-O-benzyl-l-rhamnal 8 the epimerization was less rapid and four days of epimerization was required to achieve equilibration of the epimers at room temperature. The epimerization methodology was subsequently combined with acylating enzymes in a dynamic kinetic asymmetric transformation (DYKAT), giving stereoselective acylation to the desired stereoisomers 12, 13 , and 15. The net effect of this process is an inversion of a stereogenic center on the glycal, and yields ranging from 71% to 83% of the epimer were obtained.

Simple oxidation of 3-O-silylated glycals: Application in deblocking 3-0-protected glycals

A high yielding allylic oxidation of 3-O-siIylated glycals 5-10 with the reagent system PhI(OAc)2-TMSN3 is presented. The iodine(m) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-d

Oxidation of Fully Protected Glycals by Hypervalent Iodine Reagents

A new application of organoiodine(III) is presented.Fully protected glycals are directly converted into 2,3-dihydro-4H-pyran-4-ones by benzene (PhI(OH)OTs, 1).The detailed study reveals that this conversion is independent of the rel