5627-22-5

Upstream product

• 108-86-1 bromobenzene 
• 572-09-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 
• 74372-90-0 3,4,6-tri-O-benzyl-D-glucal epoxide 
• 1011723-04-8 glucal epoxide 
• 55628-54-1 3,4,6-tri-O-benzyl-D-glucal 
• 591-50-4 iodobenzene 
• 98-80-6 phenylboronic acid 
• 841-76-9 triphenylaluminium 
• 498-07-7 levoglucosan 
• 6591-30-6 diphenylaluminum chloride 
• 32741-93-8 1,6-anhydro-β-D-glucopyranose 2,4-O-phenylboronate 
• 100-58-3 phenylmagnesium bromide 
• 1432591-76-8 2,4-di-O-tert-butyldiphenylsilyl-1-C-phenyl-β-D-glucopyranoside 
• 116391-03-8 2,4-O-dibutylstannylene-1,6-anhydro-β-D-glucopyranose 

Downstream Products

• 121315-68-2 (1S)-1-phenyl-O⁶-trityl-1,5-anhydro-D-glucitol 
• 119926-29-3 (2R,3R,4R,5S,6S)-benzoic acid 3,4,5-tribenzoyloxy-6-phenyltetrahydropyran-2-ylmethyl ester 
• 110534-58-2 (1S)-1-phenyl-O⁶-(toluene-4-sulfonyl)-1,5-anhydro-D-glucitol 
• 13231-13-5 (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)benzene 
• 112219-64-4 (2R,3R,4R,5S,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-phenyltetrahydro-2H-pyran 
• 946411-12-7 (R)-4,6-O-prop-2-enylidene-β-D-glucopyranosylbenzene 
• 891783-08-7 (2,3,4-tri-O-acetyl-6-desoxy-6-iodo-β-D-xylo-hex-5-enopyranosyl)benzene 
• 891783-07-6 (2,3,4-tri-O-acetyl-6-deoxy-6-iodo-β-D-glucopyranosyl)benzene 
• 261955-96-8 (2,3,4-tri-O-benzyl-6-desoxy-β-D-xylo-hex-5-enopyranosyl)benzene 
• 113114-66-2 1-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)-4-nitrobenzene 
• 158419-73-9 1-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)-4-retinamidobenzene 
• 158419-74-0 1-(Methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate)-4-retinamidobenzene 
• 158419-72-8 4-(Methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate)aniline 
• 158419-69-3 (Methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate)benzene 

Relevant academic research and scientific papers

Glycosyl Cross-Coupling of Anomeric Nucleophiles: Scope, Mechanism, and Applications in the Synthesis of Aryl C-Glycosides

Stereoselective manipulations at the C1 anomeric position of saccharides are one of the central goals of preparative carbohydrate chemistry. Historically, the majority of reactions forming a bond with anomeric carbon has focused on reactions of nucleophiles with saccharide donors equipped with a leaving group. Here, we describe a novel approach to stereoselective synthesis of C-aryl glycosides capitalizing on the highly stereospecific reaction of anomeric nucleophiles. First, methods for the preparation of anomeric stannanes have been developed and optimized to afford both anomers of common saccharides in high anomeric selectivities. We established that oligosaccharide stannanes could be prepared from monosaccharide stannanes via O-glycosylation with Schmidt-type donors, glycal epoxides, or under dehydrative conditions with C1 alcohols. Second, we identified a general set of catalytic conditions with Pd2(dba)3 (2.5 mol%) and a bulky ligand (JackiePhos, 10 mol%) controlling the β-elimination pathway. We demonstrated that the glycosyl cross-coupling resulted in consistently high anomeric selectivities for both anomers with mono- and oligosaccharides, deoxysugars, saccharides with free hydroxyl groups, pyranose, and furanose substrates. The versatility of the glycosyl cross-coupling reaction was probed in the total synthesis of salmochelins (siderophores) and commercial anti-diabetic drugs (gliflozins). Combined experimental and computational studies revealed that the β-elimination pathway is suppressed for biphenyl-type ligands due to the shielding of Pd(II) by sterically demanding JackiePhos, whereas smaller ligands, which allow for the formation of a Pd-F complex, predominantly result in a glycal product. Similar steric effects account for the diminished rates of cross-couplings of 1,2-cis C1-stannanes with aryl halides. DFT calculations also revealed that the transmetalation occurs via a cyclic transition state with retention of configuration at the anomeric position. Taken together, facile access to both anomers of various glycoside nucleophiles, a broad reaction scope, and uniformly high transfer of anomeric configuration make the glycosyl cross-coupling reaction a practical tool for the synthesis of bioactive natural products, drug candidates, allowing for late-stage glycodiversification studies with small molecules and biologics.

Highly Stereospecific Cross-Coupling Reactions of Anomeric Stannanes for the Synthesis of C-Aryl Glycosides

We demonstrate that configurationally stable anomeric stannanes undergo a stereospecific cross-coupling reaction with aromatic halides in the presence of a palladium catalyst with exceptionally high levels of stereocontrol. In addition to a broad substrat

β-Selective C-arylation of silyl protected 1,6-anhydroglucose with arylalanes: The synthesis of SGLT2 inhibitors

The stereoselective arylation of hydroxy protected 1,6-anhydro-β-d-glucose with arylalanes to provide β-C-arylglucosides is reported. Modification of triarylalanes, Ar3Al, with strong Br?nsted acids (HX) or AlCl3 produced more reactive arylating agents, Ar2AlX, while the incorporation of alkyl dummy ligands into the arylating agents was also viable. Me3Al and i-Bu2AlH were found useful in the in situ blocking of the C3-hydroxyl group of 2,4-di-O-TBDPS protected 1,6-anhydroglucose. The utility of the method was demonstrated by the synthesis of the SGLT2 inhibitor, canagliflozin.

β-Selective C-Arylation of Diisobutylaluminum Hydride Modified 1,6-Anhydroglucose: Synthesis of Canagliflozin without Recourse to Conventional Protecting Groups

The β-selective phenylation of benzyl and boronate protected 1,6-anhydroglucose and the direct phenylation of unprotected 1,6-anhydroglucose (10), pretreated with i-Bu2AlH, i-Bu3Al, Et3Al, Me3Al, or n-octyl3Al, with triphenylalane or aryl(chloro)alanes is reported. The utility of the unprotected version of the method is demonstrated by the synthesis of the SGLT2 inhibitor, canagliflozin (1a), from commercially available 10 in one C-C bond-forming step. This approach circumvents the need for conventional protecting groups, and therefore no formal protection and deprotection steps are required. (Chemical Presented).

Process for the Preparation of ?-C-Aryl Glucosides

The present invention provides processes for stereoselectively preparing C-arylglucosides that can be useful as synthetic building block or drugs, including SGLT2 inhibitors.

Aryl-β-C-glucosidation using glucal boronate: Application to the synthesis of tri-O-methylnorbergenin

Novel aryl-β-C-glucosidation method using glucal boronate was developed. This protocol can offer several advantages including use of non-toxic, easily handling glucal boronate as a crystalline solid and storable at room temperature for several months. Tri-O-methylnorbergenin (8,10-di-O-methylbergenin), an anti-HIV active bergenin derivative, was concisely synthesized by application of the aryl-β-C-glucosidation method.

Carbohydrate-based macrolides prepared via a convergent ring closing metathesis approach: In search for novel antibiotics

(Chemical Equation Presented) An efficient convergent approach has been developed for the construction of novel, nonnatural polysubstituted carbohydrate-based macrolides. A key step in the synthesis is the formation of the macrocyclic ring via a ring-closing metathesis reaction. The obtained macrolide analogues have been screened for biological activity against gram-positive and gram-negative bacteria, yeasts, and molds.

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.

A convergent ring-closing metathesis approach to carbohydrate-based macrolides with potential antibiotic activity

An efficient convergent approach has been developed for the construction of novel, non-natural, carbohydrate-based macrolides. The key step in the synthesis is the formation of the macrocyclic ring via a ring-closing metathesis reaction. The obtained macrolide analogues have been screened for biological activity against Gram-positive and Gram-negative bacteria, including resistant strains, yeasts, and molds.

Bicyclic carbohydrate compounds useful in the treatment of infections caused by herpesviridae

Bicyclic carbohydrates for the treatment of infections caused by herpseviridae, and in particular cytomegalovirus. The invention consists of the novel bicyclic carbohydrates the generic structure of which is: wherein R1 is either -Bn or -Ph; R2 and R3 are either -alkyl, -aryl, -allyl, or —H; R4 and R5 form a ring and are either —CH(Ph)- or —CH(aryl)- and X is either O, N or S.