Stereoselective and Regioselective Preparation of <i>C</i>‐Pentopyranosides and Formal Synthesis of Omarigliptin

Liu, Tongchao; Hou, Jian; Xie, Wuchen; You, Li; Ren, Huanming; Liang, Jianpeng; Xiong, Bing; Chen, Guohua; Cheng, Maosheng; Shen, Jingkang; Chen, Yue‐Lei

doi:10.1002/ejoc.201601074

Cited by 3 publications

(1 citation statement)

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“…Nucleophilic addition of lithium enolate or aryl lithium to sugar lactones followed by reduction using silane and BF 3 ·OEt 2 afforded the corresponding C -glycosides 591 – 594 in good yields with complete β-selectivity (Scheme ). ,,,− …”

Section: C-glycosylation With Sugar Lactonesmentioning

confidence: 99%

Recent Advances in the Chemical Synthesis of C-Glycosides

2017

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Advances in the chemical synthesis of C-pyranosides/furanosides are summarized, covering the literature from 2000 to 2016. The majority of the methods take advantage of the construction of the glycosidic C-C bond. These C-glycosylation methods are categorized herein in terms of the glycosyl donor precursors, which are commonly used in O-glycoside synthesis and are easily accessible to nonspecialists. They include glycosyl halides, glycals, sugar acetates, sugar lactols, sugar lactones, 1,2-anhydro sugars, thioglycosides/sulfoxides/sulfones, selenoglycosides/telluroglycosides, methyl glycosides, and glycosyl imidates/phosphates. Mechanistically, C-glycosylation reactions can involve glycosyl electrophilic/cationic species, anionic species, radical species, or transition-metal complexes, which are discussed as subcategories under each type of sugar precursor. Moreover, intramolecular rearrangements, such as the Claisen rearrangement, Ramberg-Bäcklund rearrangement, and 1,2-Wittig rearrangement, which usually involve concerted pathways, constitute another category of C-glycosylations. An alternative to the C-glycosylations is the formation of pyranoside/furanoside rings after construction of the predetermined glycosidic C-C bonds, which might involve cyclization of acyclic precursors or D-A cycloadditions. Throughout, the stereoselectivity in the formation of the resultant C-glycosidic linkages is highlighted.

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