Combination of 3-O-Levulinoyl and 6-O-Trifluorobenzoyl Groups Ensures α-Selectivity in Glucosylations: Synthesis of the Oligosaccharides Related to Aspergillus fumigatus α-(1 → 3)-d-Glucan

Combination of 3-O-Levulinoyl and 6-O-Trifluorobenzoyl Groups Ensures α-Selectivity in Glucosylations: Synthesis of the Oligosaccharides Related to Aspergillus fumigatus α-(1 → 3)-d-Glucan Full article

Journal

Journal of Organic Chemistry
ISSN: 1520-6904 , E-ISSN: 0022-3263

Output data

Year: 2023, Volume: 88, Number: 17, Pages: 12542-12564 Pages count : 23 DOI: 10.1021/acs.joc.3c01283

Authors

Komarova Bozhena S ¹ , Novikova Natalia S ¹ , Gerbst Alexey G ¹ , Sinitsyna Olga A ² , Rubtsova Ekaterina A ³ , Kondratyeva Elena G ³ , Sinitsyn Arkady P ^2,3 , Nifantiev Nikolay E ¹

Affiliations

1	Laboratory of Glycoconjugate Chemistry, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia
2	Department of Chemistry, M.V. Lomonosov Moscow State University, Vorobyevy Gory 1-11, Moscow 119992, Russia
3	FRC “Fundamentals of Biotechnology”, Russian Academy of Sciences, Leninsky prospect 33-2, Moscow 119071, Russia

Stereospecific α-glucosylation of primary and secondary OH-group at carbohydrate acceptors is achieved using glucosyl N-phenyl-trifluoroacetimidate (PTFAI) donor protected with an electron-withdrawing 2,4,5-trifluorobenzoyl (TFB) group at O-6 and the participating levulinoyl (Lev) group at O-3. New factors have been revealed that might explain α-stereoselectivity in the case of TFB and pentafluorobenzoyl (PFB) groups at O-6. They are of conformational nature and confirmed by DFT calculations. The potential of this donor, as well as the orthogonality of TFB and Lev protecting groups, is showcased by the synthesis of α-(1 → 3)-linked pentaglucoside corresponding to Aspergillus fumigatus α-(1 → 3)-d-glucan and of its hexasaccharide derivative, bearing β-glucosamine residue at the non-reducing end.

Komarova B.S. , Novikova N.S. , Gerbst A.G. , Sinitsyna O.A. , Rubtsova E.A. , Kondratyeva E.G. , Sinitsyn A.P. , Nifantiev N.E.
Combination of 3-O-Levulinoyl and 6-O-Trifluorobenzoyl Groups Ensures α-Selectivity in Glucosylations: Synthesis of the Oligosaccharides Related to Aspergillus fumigatus α-(1 → 3)-d-Glucan
Journal of Organic Chemistry. 2023. V.88. N17. P.12542-12564. DOI: 10.1021/acs.joc.3c01283 WOS Scopus OpenAlex

≡ Web of science:	WOS:001051326900001
≡ Scopus:	2-s2.0-85169167008
≡ OpenAlex:	W4385969034