Application of 2-Substituted Benzyl Groups in Stereoselective Glycosylation

被引：24

作者：

Buda, Szymon ^{[1
]}

Nawoj, Miroslaw ^{[1
]}

Golebiowska, Patrycja ^{[1
]}

Dyduch, Karol ^{[1
]}

Michalak, Artur ^{[1
]}

Mlynarski, Jacek ^{[1
]}

机构：

[1] Jagiellonian Univ, Fac Chem, PL-30060 Krakow, Poland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 02期

关键词：

NEIGHBORING GROUP PARTICIPATION; FOCK-SLATER CALCULATIONS; PROTECTING GROUPS; VALENCE INDEXES; OLIGOSACCHARIDE; GLYCOSIDES; CHEMISTRY; IONS;

D O I：

10.1021/jo502186f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The use of 2-O-(2-nitrobenzyl) and 2-O-(2-cyanobenzyl) groups controls stereoselective formation of 1,2-trans-glycosidic linkages via the arming participation effect. The observed stereoselectivity likely arises from the intramolecular formation of cyclic intermediate between the electron-rich substituent and the donor oxacarbenium ion providing the expected facial selectivity for attack of the glycoside acceptor. The stereodirecting effect of the 2-nitro- and 2-cyanobenzyl groups attached at the remote position (C-3, C-4, and C-6) of the donor molecule have also been investigated. To prove the postulated mechanism based on the participation effect of 2-substituted benzyl groups in the glycosylation stereoselectivity we used DFT theoretical calculation methodology.

引用

页码：770 / 780

页数：11

共 42 条

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