Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Sep 12;25(51):11831-11836.
doi: 10.1002/chem.201901969. Epub 2019 Aug 20.

Bromine-Promoted Glycosidation of Conformationally Superarmed Thioglycosides

Matteo Panza  1 , Monica Civera  2 , Jagodige P Yasomanee  1 , Laura Belvisi  2 , Alexei V Demchenko  1
Affiliations

Bromine-Promoted Glycosidation of Conformationally Superarmed Thioglycosides

Matteo Panza et al. Chemistry. .

Abstract

Presented herein is a study of the conformation and reactivity of highly reactive thioglycoside donors. The structural studies have been conducted using NMR spectroscopy and computational methods. The reactivity of these donors has been investigated in bromine-promoted glycosylations of aliphatic and sugar alcohols. Swift reaction times, high yields, and respectable 1,2-cis stereoselectivity were observed in a majority of these glycosylations.

Keywords: carbohydrate chemistry; glycosylation; stereocontrolled reactions; synthesis.

PubMed Disclaimer

Figures

Figure 1.
Figure 1.
DFT-optimized 3S1 skew-boat conformation of the 3,4-OTIPS thioglucoside β–3 (hydrogens and phenyl groups have been omitted for clarity in the ball and stick 3D-representation).
Figure 2.
Figure 2.
Conformation and stereoselectivity of β-bromides
Scheme 1.
Scheme 1.
Previous glycosidations of thioglycosides with Br2
Scheme 2.
Scheme 2.
Conversion of 3,4-di-O-TBS β-SEt glucoside β–2 into α,β-bromides 4
See this image and copyright information in PMC

References

    1. Woods RJ, Chem. Rev 2018, 118, 8005–8024; - PMC - PubMed
    2. Ruhaak LR, Xu G, Li Q, Goonatilleke E, Lebrilla CB, Chem. Rev 2018, 118, 7886–7930; - PMC - PubMed
    3. Lu G, Crihfield CL, Gattu S, Veltri LM, Holland LA, Chem. Rev 2018, 118, 7867–7885. - PMC - PubMed
    1. Wen L, Edmunds G, Gibbons C, Zhang J, Gadi MR, Zhu H, Fang J, Liu X, Kong Y, Wang PG, Chem. Rev 2018, 118, 8151–8187; - PubMed
    2. Li C, Wang LX, Chem. Rev 2018, 118, 8359–8413. - PMC - PubMed
    1. Panza M, Pistorio SG, Stine KJ, Demchenko AV, Chem. Rev 2018, 118, 8105–8150; - PMC - PubMed
    2. Nielsen MM, Pedersen CM, Chem. Rev 2018, 118, 8285–8358; - PubMed
    3. Kulkarni SS, Wang CC, Sabbavarapu NM, Podilapu AR, Liao PH, Hung SC, Chem. Rev 2018, 118, 8025–8104; - PubMed
    4. Bennett CS, Galan MC, Chem. Rev 2018, 118, 7931–7985; - PMC - PubMed
    5. Adero PO, Amarasekara H, Wen P, Bohe L, Crich D, Chem. Rev 2018, 118, 8242–8284. - PMC - PubMed
    1. Romero JAC, Tabacco SA, Woerpel KA, J. Am. Chem. Soc 2000, 122, 168–169;
    2. Ayala L, Lucero CG, Romero JAC, Tabacco SA, Woerpel KA, J. Am. Chem. Soc 2003, 125, 15521–15528; - PubMed
    3. Shenoy SR, Woerpel KA, Org. Lett 2005, 7, 1157–1160; - PubMed
    4. Baghdasarian G, Woerpel KA, J. Org. Chem 2006, 71, 6851–6858; - PubMed
    5. Billings SB, Woerpel KA, J. Org. Chem 2006, 71, 5171–5178; - PubMed
    6. Yang MT, Woerpel KA, J. Org. Chem 2009, 74, 545–553; - PMC - PubMed
    7. Beaver MG, Woerpel KA, J. Org. Chem 2010, 75, 1107–1118; - PMC - PubMed
    8. Garcia A, Sanzone JR, Woerpel KA, Angew. Chem. Int. Ed. Engl 2015, 54, 12087–12090. - PMC - PubMed
    1. Mootoo DR, Konradsson P, Udodong U, Fraser-Reid B, J. Am. Chem. Soc 1988, 110, 5583–5584;
    2. Fraser-Reid B, Udodong UE, Wu ZF, Ottosson H, Merritt JR, Rao CS, Roberts C, Madsen R, Synlett 1992, 927–942 and references therein.