TMSOTf mediated stereoselective synthesis of α-C-glycosides from unactivated aryl acetylenes

• Published in: Glycoconjugate journal Vol. 34; no. 1; pp. 13 - 20
• Main Authors: Chen, Heshan, Luo, Xiaosheng, Qiu, Saifeng, Sun, Wengjie, Zhang, Jianbo
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.02.2017
• Subjects: Acetylene - analogs & derivatives; Acetylene - chemistry; Biochemistry; Biomedical and Life Sciences; Chemistry Techniques, Synthetic - methods; Glycosides - chemical synthesis; Glycosides - chemistry; Life Sciences; Mesylates - chemistry; Original Article; Pathology; Trimethylsilyl Compounds - chemistry; Glycals; TMSOTf; glycosides; Aryl acetylenes; Metal free; C-glycosides
• ISSN: 0282-0080; 1573-4986
• DOI: 10.1007/s10719-016-9718-7

A metal free and highly stereoselective procedure for the synthesis of 2,3-unsaturated- C -glycosides has been developed between glycals and unactivated aryl acetylenes in the presence of TMSOTf through a triflated C -vinyl glycosides intermediate. The flexibility of the procedure was tested by a wide variety of glycals and unactivated aryl acetylenes (20 examples). The corresponding alkynyl C -glycosides were obtained in good yields with completely α-selectivity in a short time (<25 min). And a plausible mechanism for the synthesis of alkynyl C -glycosides was depicted.