Intramolecular and Ferrier Rearrangement Strategy for the Construction of C1‐β‐d‐xylopyranosides: Synthesis, Mechanism and Biological Activity Study

• Published in: Advanced synthesis & catalysis Vol. 361; no. 5; pp. 1012 - 1017
• Main Authors: Yao, Yuan, Xiong, Cai‐Ping, Zhong, Ya‐Ling, Bian, Guo‐Wei, Huang, Nian‐Yu, Wang, Long, Zou, Kun
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 05.03.2019; Wiley Subscription Services, Inc
• Subjects: 1,3-acyloxy migration; Biocompatibility; Biological activity; C1-glycosylation; Carboxylates; Catalysis; Chemical synthesis; Chemistry; Chemistry, Applied; Chemistry, Organic; cytotoxicity; Dichroism; Ferrier rearrangement; Gold; gold (I) catalysis; Infrared spectroscopy; Ionization; Migration; NMR; Nuclear magnetic resonance; Physical Sciences; Science & Technology; Spectrum analysis; Stereoselectivity; AMINO-ACID; gold (I) catalysis; KENDOMYCIN; 1,3-acyloxy migration; C-GLYCOSIDES; GLYCOSYLATION; Ferrier rearrangement; DERIVATIVES; cytotoxicity; C1-glycosylation
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201801423

A stereoselective synthesis of C1‐β‐d‐xylopyranoside derivatives had been developed via intramolecular 1,3‐acyloxy migration/Ferrier rearrangement stategy from readily available propargylic carboxylates and d‐xylal. A combined catalytic system of chloro(triphenylphosphine)gold(I) (Ph3PAuCl) and silver hexafluoroantimonate (AgSbF6) was found to possess the most effective of the reaction, and 20 examples tested the wide functional compatibility for these transformation. Nuclear magnetic resonance (NMR), infrared spectrum (IR), high resolution electrospray ionization mass spectroscopy (HRESIMS) and isotopic labelling experiments were utilized to investigate the C1‐glycosylation process. The relative configuration for the products was determined by two‐dimensional (2D) NMR NMR and electronic circular dichroism spectroscopy. 3‐(4,5)‐Dimethylthiahiazo(‐z‐y1)‐3,5‐diphenytetrazoliumro‐mide (MTT) cell viability assays indicated that three of them showed strong anti‐proliferative activities against human gastric cancer HGC‐27 cells with IC50 values of 17.09‐38.88 μM. This method opened up new horizons for the synthesis of bioactive C‐glycosylated molecules.