103597-21-3

Upstream product

• 108-24-7 acetic anhydride 
• 103597-20-2 methyl 2,3,4-tri-O-benzyl-D-glycero-α-D-gluco-heptopyranoside 
• 83051-88-1 methyl 6-aldehydo-2,3,4-tri-O-benzyl-α-D-glucopyranoside 
• 494853-76-8 methyl 6,7-anhydro-2,3,4-tri-O-benzyl-D/L-glycero-D-gluco-heptopyranoside 
• 888487-26-1 methyl 2,3,4-tri-O-benzyl-D/L-glycero-α-D-gluco-heptopyranoside 
• 177897-27-7 (S)-Hydroxy-((2R,3S,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-yl)-acetaldehyde 
• 103597-19-9 methyl 2,3,4-tri-O-benzyl-6,7-dideoxy-D-glycero-α-D-glucooct-7-eno-1,5-pyranoside 
• 103597-18-8 methyl-2,3,4-tri-O-benzyl-7,7,8,8-tetradehydro-7,8-dideoxy-α-D-glycero-D-gluco-octopyranoside 
• 321142-22-7 methyl 7-O-allyl-2,3,4-tri-O-benzyl-D-glycero-α-D-gluco-heptopyranoside 

Relevant academic research and scientific papers

β-Selective one-pot fluorophosphorylation of d,d -heptosylglycals mediated by selectfluor

This study describes the development of a novel procedure of glycal fluorophosphorylation applied to the synthesis of a fluorinated analogue of an important bacterial metabolite. This procedure was applied to several heptose-derived glycals, and the stereochemical outcome of the reaction was analyzed. Under optimized conditions, the reaction is β-gluco selective, but a significant amount of the α-gluco diastereomer is also generated.

Stereoselective glycal fluorophosphorylation: Synthesis of ADP-2-fluoroheptose, an inhibitor of the LPS Biosynthesis

Heptosides are found in important bacterial glycolipids such as lipopolysaccharide (LPS), the biosynthesis of which is targeted for the development of novel antibacterial agents. This work describes the synthesis of a fluorinated analogue of ADP-L-glycero-β-D-manno-heptopyranose, the donor substrate of the heptosyl transferase WaaC, which catalyzes the incorporation of this carbohydrate into LPS. Synthetically, the key step for the preparation of ADP-2F-heptose is the simultaneous and stereoselective installation of both the fluorine atom at C-2 and the phosphoryl group at C-1 through a selectfluor-mediated (selectfluor= 1-chloromethyl-4-fluorodiazoniabicyclo[2.2.2] octane bis(triflate)) electrophilic addition/nucleophilic substitution involving a heptosylglycal. Therefore, we detail in this article 1) the stereoselective preparation of the key intermediates heptosylglycals, 2) the development of a new fluorophosphorylation procedure allowing an excellent β-gluco stereoselectivity with "all-equatorial" glycals, 3) the synthesis of the target ADP-2F-heptose, and 4) some comments on the contacts observed between the fluorine atom of the final molecule and the protein in the crystallographic structure of heptosyltransferase WaaC.

Homologation of protected hexoses with Grignard C1 reagents

Derivatives of three stereoisomeric hexodialdo-1,5-pyranosides were reacted with four Grignard C1 reagents: methoxymethyl-, allyloxymethyl-, benzyloxymethyl, and dimethylphenylsilylmethyl-magnesium chlorides. Two stereoisomeric heptoses were obtained in each case in a good yield. The methyl alloside-derived heptosides were accompanied by C-5 inverted products. The addition of Grignard reagents to aldehydes 5-8 has been discussed in terms of parallel α- or β-chelated and Felkin-Anh transition states. It has been found that the silyl Grignard reagent 12 exhibits a strong preference for the formation of heptose derivatives of L-configuration at C-6. (C) 2000 Elsevier Science Ltd.

Synthesis of Methyl 2,3,4-tri-O-benzyl-D- and L-glycero-α-D-glucoheptopyranosides

Title compounds 8 and 17 have been synthesized from methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-D- and L-glycero-α-D-gluco-oct-7-ynopyranosides (6 and 15 respectively) in three steps: hydrogenation of the triple bond, ozonolytic cleavage of the resulting double