Catalytic Site-Selective Acylation of Carbohydrates Directed by Cation–n Interaction

Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calcula...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2017-03, Vol.139 (12), p.4346-4349
Main Authors: Xiao, Guozhi, Cintron-Rosado, Gabriel A, Glazier, Daniel A, Xi, Bao-min, Liu, Can, Liu, Peng, Tang, Weiping
Format: Article
Language:English
Subjects:
Acylation
Carbohydrates - chemistry
Catalysis
Cations - chemistry
Models, Molecular
Molecular Conformation
Quantum Theory
Tetramisole - analogs & derivatives
Tetramisole - chemistry
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Summary:Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calculations indicate that the key determining factor for the selectivity is the presence or absence of a cation–n interaction between the cation in the acylated catalyst and an appropriate lone pair in the substrate. DFT calculations also provided a predictive model for site-selectivity and this model is validated by various substrates.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b01412