3682-06-2

Upstream product

• 60-29-7 diethyl ether 
• 13242-53-0 acetobromomannose 
• 2674-04-6 diphenyl cadmium 
• 591-51-5 phenyllithium 
• 108-88-3 toluene 
• 572-09-8 2,3,4,6-tetra-O-acetyl-D-mannopyranosyl bromide 
• 108-24-7 acetic anhydride 
• 63598-21-0 α-D-mannopyranosylbenzene 
• 83-87-4 β-D-mannopyranose pentaacetate 
• 572-10-1 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl chloride 
• 591-50-4 iodobenzene 
• 108-86-1 bromobenzene 
• 572-09-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 63598-21-0 α-D-mannopyranosylbenzene 
• 882302-30-9 (2R,3S,4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-2-phenyl-hexahydro-1,5,7,9-tetraoxa-6,8-disila-benzocyclooctene-3,4-diol 
• 882302-28-5 (1S)-1-phenyl-1,5-anhydro-D-mannitol 
• 882302-29-6 (2S,3S,4R,4aS,10aR)-6,6,8,8-Tetraisopropyl-2-phenyl-hexahydro-1,5,7,9-tetraoxa-6,8-disila-benzocyclooctene-3,4-diol 

Relevant academic research and scientific papers

Diastereoselective Synthesis of Aryl C-Glycosides from Glycosyl Esters via C?O Bond Homolysis

C-aryl glycosyl compounds offer better in vivo stability relative to O- and N-glycoside analogues. C-aryl glycosides are extensively investigated as drug candidates and applied to chemical biology studies. Previously, C-aryl glycosides were derived from lactones, glycals, glycosyl stannanes, and halides, via methods displaying various limitations with respect to the scope, functional-group compatibility, and practicality. Challenges remain in the synthesis of C-aryl nucleosides and 2-deoxysugars from easily accessible carbohydrate precursors. Herein, we report a cross-coupling method to prepare C-aryl and heteroaryl glycosides, including nucleosides and 2-deoxysugars, from glycosyl esters and bromoarenes. Activation of the carbohydrate substrates leverages dihydropyridine (DHP) as an activating group followed by decarboxylation to generate a glycosyl radical via C?O bond homolysis. This strategy represents a new means to activate alcohols as a cross-coupling partner. The convenient preparation of glycosyl esters and their stability exemplifies the potential of this method in medicinal chemistry.

Stereoselective Preparation of α- C-Vinyl/Aryl Glycosides via Nickel-Catalyzed Reductive Coupling of Glycosyl Halides with Vinyl and Aryl Halides

Facile preparation of the α-C-vinyl and -aryl glycosides has been developed via mild Ni-catalyzed reductive vinylation and arylation of C1-glycosyl halides with vinyl/aryl halides. Good to high α-selectivities were achieved for C-glucosides, galactosides, maltoside, and mannosides, which were dictated by the employment of pyridine type ligands. As such, the present work represents unprecedented control for a high level of α-selectivity for C-vinyl-glucosides using cross-coupling approaches and offers hitherto optimal α-selective preparation of C-aryl glucosides via catalyst-controlled coupling strategies.

Synthesis of Aryl C-Glycosides via Iron-Catalyzed Cross Coupling of Halosugars: Stereoselective Anomeric Arylation of Glycosyl Radicals

We have developed a novel diastereoselective iron-catalyzed cross-coupling reaction of various glycosyl halides with aryl metal reagents for the efficient synthesis of aryl C-glycosides, which are of significant pharmaceutical interest due to their biological activities and resistance toward metabolic degradation. A variety of aryl, heteroaryl, and vinyl metal reagents can be cross-coupled with glycosyl halides in high yields in the presence of a well-defined iron complex, composed of iron(II) chloride and a bulky bisphosphine ligand, TMS-SciOPP. The chemoselective nature of the reaction allows the use of synthetically versatile acetyl-protected glycosyl donors and the incorporation of various functional groups on the aryl moieties, producing a diverse array of aryl C-glycosides, including Canagliflozin, an inhibitor of sodium-glucose cotransporter 2 (SGLT2), and a prevailing diabetes drug. The cross-coupling reaction proceeds via generation and stereoselective trapping of glycosyl radical intermediates, representing a rare example of highly stereoselective carbon-carbon bond formation based on iron catalysis. Radical probe experiments using 3,4,6-tri-O-acetyl-2-O-allyl-α-d-glucopyranosyl bromide (8) and 6-bromo-1-hexene (10) confirm the generation and intermediacy of the corresponding glycosyl radicals. Density functional theory (DFT) calculations reveal that the observed anomeric diastereoselectivity is attributable to the relative stability of the conformers of glycosyl radical intermediates. The present cross-coupling reaction demonstrates the potential of iron-catalyzed stereo- and chemoselective carbon-carbon bond formation in the synthesis of bioactive compounds of certain structural complexity.

Triphenylphosphine: A catalyst for the synthesis of C-aryl furanosides from furanosyl halides

An array of C-aryl furanosides was prepared in good yields from furanosyl halides and aryl Grignard reagents in Et2O using PPh3 as a catalyst.

Diastereoselective metal-catalyzed synthesis of C-aryl and C-vinyl glycosides

Cobalt, the catalyst of choice: The diastereoselective cobalt-catalyzed cross-coupling of 1-bromo glycosides and aryl or vinyl Grignard reagents is described. A convenient and inexpensive catalyst, [Co(acac)3]/tmeda (acac=acetylacetonate, tmeda=N,N'-tetramethylethylenediamine), gives full α selectivity in the mannose and galactose series, and an α selectivity in the glucose series with α/β ratios of 1.3:1-3:1. Copyright

Diastereoselective metal-catalyzed synthesis of C-aryl and C-vinyl glycosides

Cobalt, the catalyst of choice: The diastereoselective cobalt-catalyzed cross-coupling of 1-bromo glycosides and aryl or vinyl Grignard reagents is described. A convenient and inexpensive catalyst, [Co(acac)3]/tmeda (acac=acetylacetonate, tmeda=N,N'-tetramethylethylenediamine), gives full α selectivity in the mannose and galactose series, and an α selectivity in the glucose series with α/β ratios of 1.3:1-3:1. Copyright

Synthesis and screening of bicyclic carbohydrate-based compounds: A novel type of antivirals

A small library of bicyclic carbohydrate derivatives was synthesized and screened. A strong and selective activity against cytomegalovirus was found. Structure-activity relationship for this new type of antivirals is discussed.

Epoxidation and bis-hydroxylation of C-phenyl-Δ2,3- glycopyranosides

Epoxidation and cis-hydroxylation of C-phenyl-Δ2,3 -glycopyranosides have been carried out with a view to developing C-aryl glycoside synthesis. Epoxidation of (2,3-dideoxy-D-erythro-hex-2-enopyranosyl) benzene and (6-O-tert-butyldimethylsilyl-

Synthesis of C-aryl-Δ2,3-glycopyranosides via uncatalyzed addition of triarylindium reagents to glycals

2,3-Unsaturated-C-aryl glycopyranosides are important intermediates in the synthesis of medicinally important C-aryl glycosides. Treatment of glycal acetates with triarylindiums in ether at room temperature gives good yields of C-aryl-Δ2,3-glyc