Organic Letters
Letter
(4) (a) Ranade, S. C.; Demchenko, A. V. Carbohydr. Res. 2015, 403,
115−122. (b) Yasomanee, J. P.; Demchenko, A. V. Trends Glycosci.
Glycotechnol. 2013, 25, 13−42.
SPh group with NBS/Cu(OTf)2, thus demonstrating the
orthogonal activation of SEt over SPh leaving groups with
MSH at ambient temperature. This might find useful applications
in one-pot oligosaccharide synthesis.
(5) Ranade, S. C.; Demchenko, A. V. J. Carbohydr. Chem. 2013, 32, 1−
43.
In summary, the selective activation of different 1-thioglyco-
side donors by the N+-thiophilic reagent O-mesitylenesulfonyl-
hydroxylamine as a promoter has been thoroughly studied. The
resulting 1-O-sulfonylmesitylene intermediate species were
(6) (a) Premathilake, H. D.; Demchenko, A. V. Top. Curr. Chem. 2010,
301, 189−221. (b) Codee, J. D. C.; Litjens, R. E. J. N.; van den Bos, L. J.;
Overkleeft, H. S.; van der Marel, G. A. Chem. Soc. Rev. 2005, 34, 769−
782. (c) Kamat, M. N.; Demchenko, A. V. Org. Lett. 2005, 7, 3215−
3218. (d) Kaeothip, S.; Demchenko, A. V. J. Org. Chem. 2011, 76, 7388−
7398.
(7) (a) Bernardes, G. J. L.; Chalker, J. M.; Errey, J. C.; Davis, B. G. J.
Am. Chem. Soc. 2008, 130, 5052−5053. (b) Bizet, V.; Hendriks, C. M.
M.; Bolm, C. Chem. Soc. Rev. 2015, 44, 3378−3390.
(8) Gama, Y.; Kawabata, Y.; Kusakabe, I. J. Jpn. Oil Chem. Soc. 1994, 43,
520−523.
1
detected by H NMR for monosaccharides 2−4 and isolated/
characterized in the presence of a fluorine atom at C2 in the D-
mannose and D-glucose series. We showed that MSH is the
thiophilic species, but a soft Lewis acid such as Cu(OTf)2 is
necessary for a successful glycosylation reaction. Furthermore, a
proof-of-principle study demonstrated the specific activation of
anomeric S-ethyl leaving groups in the presence of S-phenyl
groups, and this enabled the sequential preparation of a
trisaccharide. As this differentiation can be performed at ambient
temperature, this protocol may find utility for one-pot
oligosaccharide synthesis.
(9) (a) Issa, J. P.; Bennett, C. S. J. Am. Chem. Soc. 2014, 136, 5740−
5744. (b) Issa, J. P.; Lloyd, D.; Steliotes, E.; Bennett, C. S. Org. Lett.
2013, 15, 4170−4173.
(10) D’Angelo, K. A.; Taylor, M. S. J. Am. Chem. Soc. 2016, 138,
11058−11066.
(11) Matsuo, J.-I.; Kozai, T.; Ishibashi, H. Org. Lett. 2006, 8, 6095−
6098.
ASSOCIATED CONTENT
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(12) (a) Mootoo, D. R.; Konradsson, P.; Udodong, U.; Fraser-Reid, B.
J. Am. Chem. Soc. 1988, 110, 5583−5584. (b) Smoot, J. T.; Demchenko,
A. V. J. Org. Chem. 2008, 73, 8838−8850.
S
* Supporting Information
The Supporting Information is available free of charge on the
(13) Hasty, S. J.; Bandara, M. D.; Rath, N. P.; Demchenko, A. V. J. Org.
Chem. 2017, 82, 1904−1911.
Detailed experimental procedures and characterization
(14) Hasty, S. J.; Kleine, M. A.; Demchenko, A. V. Angew. Chem., Int.
Ed. 2011, 50, 4197−4201.
(15) Nigudkar, S. S.; Wang, T.; Pistorio, S. G.; Yasomanee, J. P.; Stine,
K. J.; Demchenko, A. V. Org. Biomol. Chem. 2017, 15, 348−359.
AUTHOR INFORMATION
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́ ́
(16) Salvado, M.; Amgarten, B.; Castillon, S.; Bernardes, G. J. L.;
Boutureira, O. Org. Lett. 2015, 17, 2836−2839.
Corresponding Authors
(17) (a) Frihed, T. G.; Bols, M.; Pedersen, C. M. Chem. Rev. 2015, 115,
ORCID
4963−5013. (b) Bohe,
́
L.; Crich, D. Carbohydr. Res. 2015, 403, 48−59.
(18) (a) Smith, R.; Muller-Bunz, H.; Zhu, X. Org. Lett. 2016, 18, 3578−
̈
3581. (b) Crich, D.; Li, M. Org. Lett. 2007, 9, 4115−4118.
(19) (a) Li, X.; Zhu, J. J. Carbohydr. Chem. 2012, 31, 284−324.
(b) Jensen, K. J. J. Chem. Soc., Perkin Trans. 1 2002, 2219−2233.
(20) Yu, Y.; Xiong, D.-C.; Mao, R.-Z.; Ye, X.-S. J. Org. Chem. 2016, 81,
7134−7138.
́
́
(21) Chu, A.-H. A.; Minciunescu, A.; Bennett, C. S. Org. Lett. 2015, 17,
6262−6265.
Gonca
̧
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank the European Commission (Marie Curie CIG and
Marie Skłodowska-Curie ITN project GlycoVax to G.J.L.B. and
A.K.; Marie Skłodowska-Curie IEF to E.J.M.), MINECO (RYC-
2015-17705 to O.B. and CTQ2015-70524-R and RYC-2013-
14706 to G.J.O.), FCT Portugal (FCT Investigator to G.J.L.B.),
the European Regional Development Fund, Generalitat de
Catalunya (M.S.), and the Universitat Rovira i Virgili (Martı
́
̀
Franques Research Fellowship Programme to J.M.) for financial
support. BIFI (Memento cluster) is acknowledged for computer
support. G.J.L.B. is a Royal Society University Research Fellow
and holds an ERC Starting Grant (TagIt).
REFERENCES
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(1) Ohtsubo, K.; Marth, J. D. Cell 2006, 126, 855−867.
(2) Adamo, R.; Nilo, A.; Castagner, B.; Boutureira, O.; Berti, F.;
Bernardes, G. J. L. Chem. Sci. 2013, 4, 2995−3008.
(3) Bernardes, G. J. L.; Castagner, B.; Seeberger, P. H. ACS Chem. Biol.
2009, 4, 703−713.
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