C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation.

C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation. Research Abstract Details 

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C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation. Abstract Text:

Matthew G Beaver,Susan B Billings,K A Woerpel,Matthew G Beaver,Susan B Billings,K A Woerpel,

Nucleophilic substitution reactions of C-4 sulfur-substituted tetrahydropyran acetals revealed that neighboring-group participation does not control product formation. Spectroscopic evidence for the formation of an intermediate sulfonium ion is provided, as are data from nucleophilic substitution reactions demonstrating that products are formed from oxocarbenium ion intermediates. The selectivity was not sensitive to solvent or to which Lewis acid was employed. The identity of the heteroatom at the C-4 position also did not significantly impact diastereoselectivity. Consequently, neighboring-group participation was not responsible for the formation of either the major or the minor products. These studies implicate a Curtin-Hammett kinetic scenario in which the formation of a low-energy intermediate does not necessitate its involvement in the product-forming pathway.

C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation. Publishing Authors By Initials

MG Beaver,SB Billings,KA Woerpel,MG Beaver,SB Billings,KA Woerpel,

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C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 130

Page Numbers: 2082-6

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 1520-5126

DAY: 24

MONTH: 01

YEAR: 2008

C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

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Grant and Affiliation Information for C-Glycosylation Reactions of Sulfur-Substituted Glycosyl Donors: Evidence against the Role of Neighboring-Group Participation.

AFFILIATION: Department of Chemistry, University of California, Irvine, California 92697-2025.

Country: United States

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MEDLINETA: J Am Chem Soc

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