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Review
. 2019 Jan 1:471:64-77.
doi: 10.1016/j.carres.2018.11.012. Epub 2018 Nov 23.

Recent advances in site-selective functionalization of carbohydrates mediated by organocatalysts

Stephanie A Blaszczyk  1 , Timothy C Homan  2 , Weiping Tang  3
Affiliations
Review

Recent advances in site-selective functionalization of carbohydrates mediated by organocatalysts

Stephanie A Blaszczyk et al. Carbohydr Res. .

Abstract

As one of the four fundamental building blocks of life, carbohydrates assume varied and expansive roles in biological contexts. More in-depth understanding of carbohydrates and their interactions, however, is often restricted by our inability to synthesize and subsequently functionalize them in a site-selective manner. This review will summarize recent advances in the site-selective functionalization of carbohydrates using organocatalysts, including achiral catalysts, chiral nucleophilic bases, chiral N-heterocyclic carbenes, and chiral phosphoric acids, with an emphasis on the catalytic nature in each case. As in many endeavors, taking an alternative approach can often lead to success, and selected examples of these achievements will be highlighted as well.

Keywords: Carbohydrate; Organocatalysis; Site-selective functionalization.

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Figures

Scheme 1:
Scheme 1:
Dong and Ren’s use of DIPEA and an anhydride to self-catalyze site-selective acylation.
Scheme 2:
Scheme 2:
Schmidt’s use of benzoyl cyanide (BzCN) to acylate the axial hydroxyl group in cis-1,2-diols.
Scheme 3:
Scheme 3:
Schmidt and Peng’s one-pot synthesis of unprotected C3-OH monosaccharides via site-selective acylation.
Scheme 4:
Scheme 4:
Tang’s use of chiral benzotetramisole (BTM) catalysts to differentiate trans-1,2-diols for acylation.
Scheme 5:
Scheme 5:
Kawabata’s use of in situ counter anion exchange to promote quick site-selective acylation.
Scheme 6:
Scheme 6:
Kirsch’s use of a DMAP-based amino acid catalyst for site-selective acylation.
Scheme 7:
Scheme 7:
Sundén’s use of ionic liquids to promote a NHC-catalyzed site-selective functionalization of carbohydrates.
Scheme 8:
Scheme 8:
Studer’s use of oxidative NHC catalysis to perform site-selectively acylation.
Scheme 9:
Scheme 9:
Nagorny’s use of chiral phosphoric acids to site-selectively glycosylate 6-deoxy-erythronolide B.
Scheme 10:
Scheme 10:
Galan’s synergistic catalysis using thiourea and a chiral phosphoric acid to promote stereoselective glycosylations.
Scheme 11:
Scheme 11:
Taylor’s use of boronic acid esters as transient protecting groups and activators for site-selective glycosylation.
Scheme 12:
Scheme 12:
Taylor’s use of boronic acid esters to promote copper (II) mediated O-arylation of carbohydrates.
Scheme 13:
Scheme 13:
Makino’s use of boronic acid esters for site-selective sulfation.
Scheme 14:
Scheme 14:
Moitessier’s use of boronic acid esters to site-selectively acylate unprotected carbohydrates
Scheme 15:
Scheme 15:
O’Doherty’s use of a dual B-/Pd- catalyzed glycosylation to synthesize the mezzettiasides.
See this image and copyright information in PMC

References

    1. Wang H-Y, Blaszczyk SA, Xiao G, Tang W, Chiral reagents in glycosylation and modification of carbohydrates, Chem. Soc. Rev 47 (2017) 681–701. - PubMed
    1. Seeberger PH, Automated synthesis of oligosaccharides as a basis for drug discovery, Nat. Rev. Drug Discov 4 (2005) 751–763. - PubMed
    1. Panza M, Pistorio SG, Stine KJ, Demchenko AV, Automated chemical oligosaccharide synthesis: novel approach to traditional challenges, Chem. Rev 118 (17) (2018) 8105–8150. - PMC - PubMed
    2. Hsu CH, Hung S-C, Wu C-Y, Wong C-H, Toward automated oligosaccharide synthesis, Angew. Chem. Int. Ed 50 (2011) 11872–11939. - PubMed
    3. Seeberger PH, Automated oligosaccharide synthesis, Chem. Soc. Rev 37 (2008) 19–28. - PubMed
    1. Wen L, Edmunds G, Gibbons C, Zhang J, Gadi MR, Zhu H, Fang J, Liu X, Kong Y, Wang PG, Towards automatic enzymatic synthesis of oligosaccharides, Chem. Rev 118 (17) (2018) 8151–8187. - PubMed
    1. Lawandi J, Rocheleau S, Moitessier N, Regioselective acylation, acylation, silylation, and glycosylation of monosaccharides, Tetrahedron 72 (2016) 6283–6319.

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