Stereospecific Synthesis of α- and β-C-Glycosides from Glycosyl Sulfoxides:  Scope and Limitations

C-Glycosides derived from α-l-fuco-, α-d-gluco-, β-d-gluco-, and α-d-mannopyranose have been synthesized from the corresponding glycosyl phenyl sulfoxide through phenylsulfinyl−lithium exchange, to generate an anomeric carbanion, and subsequent reaction with a carbon electrophile. The reactions were...

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Bibliographic Details
Published in:Journal of organic chemistry 2001-03, Vol.66 (5), p.1768-1774
Main Authors: Carpintero, Mercedes, Nieto, Inés, Fernández-Mayoralas, Alfonso
Format: Article
Language:English
Subjects:
Glycosides - chemical synthesis
Glycosides - chemistry
Magnetic Resonance Spectroscopy
Sulfoxides - chemistry
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Summary:C-Glycosides derived from α-l-fuco-, α-d-gluco-, β-d-gluco-, and α-d-mannopyranose have been synthesized from the corresponding glycosyl phenyl sulfoxide through phenylsulfinyl−lithium exchange, to generate an anomeric carbanion, and subsequent reaction with a carbon electrophile. The reactions were stereospecific and proceeded with retention of the configuration at the anomeric center. Improved yields of C-glycosides were obtained by an inverse addition protocol. Trapping of the anomeric carbanion with aldehydes gave best results. Reaction with ketones, chloroformates, nitriles, and alkyl halides was also explored. Mechanistic aspects of the reaction are discussed.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0014515