2,3-Carbamate mannosamine glycosyl donors in glycosylation reactions of diacetone-D-glucose. An experimental and theoretical study

被引：5

作者：

Morelli, Laura ^{[1
]}

Legnani, Laura ^{[2
]}

Ronchi, Silvia ^{[1
]}

Confalonieri, Laura ^{[3
]}

Imperio, Daniela ^{[3
]}

Toma, Lucio ^{[2
]}

Compostella, Federica ^{[1
]}

机构：

[1] Univ Milan, Dipartimento Biotecnol Med & Med Traslaz, Via Saldini 50, I-20133 Milan, Italy

[2] Univ Pavia, Dipartimento Chim, Via Taramelli 12, I-27100 Pavia, Italy

[3] Univ Piemonte Orientale, Dipartimento Sci Farm, Lgo Donegani 2, I-28100 Novara, Italy

来源：

CARBOHYDRATE RESEARCH | 2021年 / 509卷

关键词：

Carbohydrates; Glycosylation; 12-Cis glycosides; beta-mannosides; DFT calculations; BETA-MANNOPYRANOSIDES; STEREOSELECTIVE-SYNTHESIS; OLIGOSACCHARIDE SYNTHESIS; COMBINATION; MECHANISMS; ANHYDRIDE; SYSTEM;

D O I：

10.1016/j.carres.2021.108421

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The role of the cyclic 2,3-N,O-carbamate protecting group in directing the selectivity of mannosylation reactions of diacetone-D-glucose, promoted by BSP/Tf2O via a-triflate intermediates, has been investigated through a combined computational and experimental approach. DFT calculations were used to locate the transition states leading to the alpha or beta anomers. These data indicate the preferential formation of the beta-adduct with mannosyl donors either equipped with the 4,6-O-benzylidene protection or without it. The synthetic results confirmed this preference, showing in both cases an alpha/beta selectivity of 4:6. This highlights a role for the 2,3-N,O-carbamate in sharp contrast with what described in the case of 2,3-O-carbonate mannosyl donors.

引用

页数：9

共 30 条

[1]

Abdel-Rahman AAH, 2002, ANGEW CHEM INT EDIT, V41, P2972, DOI 10.1002/1521-3773(20020816)41:16<2972::AID-ANIE2972>3.0.CO

[2]

2-4

[3] The Experimental Evidence in Support of Glycosylation Mechanisms at the SN1-SN2 Interface [J].