Catalyst-Controlled Stereoselective O-Glycosylation: Pd(0) vs Pd(II)

被引：52

作者：

Yao, Hui ^{[1
]}

Zhang, Shasha ^{[1
]}

Leng, Wei-Lin ^{[1
]}

Leow, Min-Li ^{[1
]}

Xiang, Shaohua ^{[1
]}

He, Jingxi ^{[1
]}

Liao, Hongze ^{[1
]}

Hoang, Kim Le Mai ^{[1
]}

Liu, Xue-Wei ^{[1
]}

机构：

[1] Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, 21 Nanyang Link, Singapore 637371, Singapore

来源：

ACS CATALYSIS | 2017年 / 7卷 / 08期

关键词：

glycosylation; palladium; decarboxylative allylation; glycal; reaction mechanism; GLYCOSIDE-BOND FORMATION; DE-NOVO SYNTHESIS; DECARBOXYLATIVE ALLYLATION; DONORS; GLYCALS;

D O I：

10.1021/acscatal.7b01630

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Stereoselective construction of various O-glycosidic bonds was first achieved by different palladium sources using 3,4-O-carbonate galactal as the donor to reach yields up to 95% under mild conditions. With Pd(II) catalyst coordination of this glycal donor from the beta-face directed by carbonate group, hard nucleophiles (aliphatic alcohols) gave beta-glycosides and alpha-glycosides were obtained from soft nucleophiles (phenols). In contrast, with the Pd(0) catalyst coordinating the donor from the beta-face due to steric effect, both hard and soft acceptors could only generate beta-glycosides via hydrogen-bond-mediated aglycone delivery.

引用

页码：5456 / 5460

页数：5

共 23 条

[1] De novo synthesis of oligosaccharides using a palladium-catalyzed glycosylation reaction [J].