94940-18-8

Upstream product

• 932-31-0 ortho-tolylmagnesium bromide 
• 4451-35-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl chloride 
• 108-24-7 acetic anhydride 
• 100-44-7 benzyl chloride 
• 4451-36-9 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 
• 572-09-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 
• 95-46-5 2-methylphenyl bromide 

Downstream Products

• 116603-92-0 (1S)-tetra-O-acetyl-1-(2-chloromethyl-phenyl)-1,5-anhydro-D-glucitol 
• 116567-07-8 (1S)-tetra-O-acetyl-1-(5-chloro-2-methyl-phenyl)-1,5-anhydro-D-glucitol 
• 116977-03-8 (1S)-tetra-O-acetyl-1-(5-bromo-2-methyl-phenyl)-1,5-anhydro-D-glucitol 

Relevant academic research and scientific papers

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.

Remarkable β-selectivity in the synthesis of β-1-C- arylglucosides: Stereoselective reduction of acetyl-protected methyl 1-C-arylglucosides without acetoxy-group participation

(Chemical Equation Presented) An efficient and practical process to generate β-C-arylglucoside derivatives was achieved. The process described involves Lewis acid mediated ionic reduction of a peracetylated 1-C-aryl methyl glucoside derived from the addit

REACTION OF GLYCOSYL HALIDES WITH BENZYL GRIGNARD REAGENTS: UNEXPECTED o-TOLYL ALKYLATION OF TETRA-O-ACETYLGLUCOPYRANOSYL BROMIDE AND DIRECT SYNTHESIS OF (β-GLYCOSYL)PHENYLMETHANES

The synthesis of (β-glycosyl)phenylmethanes by Grignard alkylation of glycosyl halides is investigated.Reaction of tetra-O-acetylglucopyranosyl bromide with benzylmagnesium chloride gave a good yield of a 3:1 mixture of 2-(β-D-glucopyranosyl)toluene and (β-glucosyl)phenylmethane.The requirement for an equatorial 2-acetoxy group and 6-acetoxymethyl group for the formation of the unexpected o-tolyl rearrangement product is explored by using xylosyl, mannosyl, and 2-deoxyglucosyl halides as substrates for the alkylation.Synthesis of (β-glucosyl)phenylmethane by alkylation of 2,3,4,6-tetra-O-benzylglucosyl bromide with benzylmagnesium chloride is also presented.