Large-Scale Synthesis of Crystalline 1,2,3,4,6,7-Hexa--acetyl-l-α-d--heptopyranose

Overview

Journal European J Org Chem

Specialty Biochemistry

Date 2015 Jun 23

PMID 26097405

Citations 9

Authors

Christian Stanetty

Ian R Baxendale

Affiliations

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Abstract

The higher-carbon sugar l--d--heptose is a major constituent of the inner core region of the lipopolysaccharide (LPS) of many Gram-negative bacteria. All preparative routes used to date require multiple steps, and scalability has been rarely addressed. Here a highly practical synthesis of crystalline 1,2,3,4,6,7-hexa--acetyl-l--α-d--heptopyranose by a simple four-step sequence starting from l-lyxose is disclosed. Only two recrystallisations are required and the process was demonstrated on a >100 mmol scale, yielding 41 g of the target compound.

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References

Stepowska H, Zamojski A . From methyl mannosides to methyl octosides by a stepwise homologation with Grignard C(1) reagents. Carbohydr Res. 2001; 332(4):429-38. DOI: 10.1016/s0008-6215(01)00103-3. View

Yamasaki R, Nagahara K, Kishimoto K, Takajyo A . Synthesis of a spacer-linked derivative of heptopyranosyl(α1-3)heptopyranose expressed in lipooligosaccharide and lipopolysaccharide. Biosci Biotechnol Biochem. 2012; 76(4):772-7. DOI: 10.1271/bbb.110903. View

Di Padova F, Brade H, Barclay G, Poxton I, Liehl E, SCHUETZE E . A broadly cross-protective monoclonal antibody binding to Escherichia coli and Salmonella lipopolysaccharides. Infect Immun. 1993; 61(9):3863-72. PMC: 281087. DOI: 10.1128/iai.61.9.3863-3872.1993. View

Anish C, Guo X, Wahlbrink A, Seeberger P . Plague detection by anti-carbohydrate antibodies. Angew Chem Int Ed Engl. 2013; 52(36):9524-8. DOI: 10.1002/anie.201301633. View

Yang Y, Oishi S, Martin C, Seeberger P . Diversity-oriented synthesis of inner core oligosaccharides of the lipopolysaccharide of pathogenic Gram-negative bacteria. J Am Chem Soc. 2013; 135(16):6262-71. DOI: 10.1021/ja401164s. View

Wakarchuk W, Schur M, St Michael F, Li J, Eichler E, Whitfield D . Characterization of the alpha-1,2-N-acetylglucosaminyltransferase of Neisseria gonorrhoeae, a key control point in lipooligosaccharide biosynthesis. Glycobiology. 2004; 14(6):537-46. DOI: 10.1093/glycob/cwh074. View

Palmelund A, Madsen R . Chain elongation of aldoses by indium-mediated coupling with 3-bromopropenyl esters. J Org Chem. 2005; 70(20):8248-51. DOI: 10.1021/jo051297s. View

Schiaffo C, Dussault P . Ozonolysis in solvent/water mixtures: direct conversion of alkenes to aldehydes and ketones. J Org Chem. 2008; 73(12):4688-90. DOI: 10.1021/jo800323x. View

Holst O, Brade H, Dziewiszek K, Zamojski A . G.l.c.-m.s. of partially methylated and acetylated derivatives of L-glycero-D-manno- and D-glycero-D-manno-heptopyranoses and -heptitols. Carbohydr Res. 1990; 204:1-9. DOI: 10.1016/0008-6215(90)84016-n. View

10.

Garegg P, Oscarson S, Szonyi M . Synthesis of methyl 3-O-(alpha-D-glucopyranosyl)-7-O-(L-glycero-alpha-D- manno-heptopyranosyl)-L-glycero-alpha-D-manno-heptopyranoside. Carbohydr Res. 1990; 205:125-32. DOI: 10.1016/0008-6215(90)80133-n. View

11.

Holst O . The structures of core regions from enterobacterial lipopolysaccharides - an update. FEMS Microbiol Lett. 2007; 271(1):3-11. DOI: 10.1111/j.1574-6968.2007.00708.x. View

12.

Lombardo M, Morganti S, Trombini C . The hydroboration of propargyl bromide. Simple one-Pot three-component routes to (Z)-1-bromoalk-1-en-4-ols and to anti-homoallylic alcohols. J Org Chem. 2000; 65(25):8767-73. DOI: 10.1021/jo005633a. View

13.

Zamyatina A, Gronow S, Puchberger M, Graziani A, Hofinger A, Kosma P . Efficient chemical synthesis of both anomers of ADP L-glycero- and D-glycero-D-manno-heptopyranose. Carbohydr Res. 2003; 338(23):2571-89. DOI: 10.1016/s0008-6215(03)00319-7. View

14.

Marchetti R, Malinovska L, Lameignere E, Adamova L, De Castro C, Cioci G . Burkholderia cenocepacia lectin A binding to heptoses from the bacterial lipopolysaccharide. Glycobiology. 2012; 22(10):1387-98. DOI: 10.1093/glycob/cws105. View

15.

Lombardo M, Girotti R, Morganti S, Trombini C . A new protocol for the acetoxyallylation of aldehydes mediated by indium in THF. Org Lett. 2001; 3(19):2981-3. DOI: 10.1021/ol016315g. View

16.

Ohara T, Adibekian A, Esposito D, Stallforth P, Seeberger P . Towards the synthesis of a Yersinia pestis cell wall polysaccharide: enantioselective synthesis of an L-glycero-D-manno-heptose building block. Chem Commun (Camb). 2010; 46(23):4106-8. DOI: 10.1039/c000784f. View

17.

Artner D, Stanetty C, Mereiter K, Zamyatina A, Kosma P . Crystal and molecular structure of methyl L-glycero-α-D-manno-heptopyranoside, and synthesis of 1→7 linked L-glycero-D-manno-heptobiose and its methyl α-glycoside. Carbohydr Res. 2011; 346(13):1739-46. PMC: 3252701. DOI: 10.1016/j.carres.2011.05.033. View

18.

Zamyatina , Gronow , Oertelt , Puchberger , Brade , Kosma . Efficient Chemical Synthesis of the Two Anomers of ADP-L-glycero- and D-glycero-D-manno-Heptopyranose Allows the Determination of the Substrate Specificities of Bacterial Heptosyltransferases This work was supported by grants from FWF (grant nos..... Angew Chem Int Ed Engl. 2000; 39(22):4150-4153. DOI: 10.1002/1521-3773(20001117)39:22<4150::aid-anie4150>3.0.co;2-a. View

19.

Stanetty C, Walter M, Kosma P . Convergent synthesis of 4-O-phosphorylated L-glycero-D-manno-heptosyl lipopolysaccharide core oligosaccharides based on regioselective cleavage of a 6,7-O-tetraisopropyldisiloxane-1,3-diyl protecting group. J Org Chem. 2013; 79(2):582-98. PMC: 3898546. DOI: 10.1021/jo402312x. View

20.

Durka M, Buffet K, Iehl J, Holler M, Nierengarten J, Vincent S . The inhibition of liposaccharide heptosyltransferase WaaC with multivalent glycosylated fullerenes: a new mode of glycosyltransferase inhibition. Chemistry. 2011; 18(2):641-51. DOI: 10.1002/chem.201102052. View