title: Catalytic Site-Selective Acylation of Carbohydrates Directed by Cation-n Interaction.
abstract: 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.
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
authors.forename: Guozhi
authors.initials: G
authors.lastname: Xiao
authors.affiliation: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
authors.forename: Gabriel A
authors.initials: GA
authors.lastname: Cintron-Rosado
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.|Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Glazier
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
authors.forename: Bao-Min
authors.initials: BM
authors.lastname: Xi
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
authors.forename: Can
authors.initials: C
authors.lastname: Liu
authors.affiliation: Department of Chemistry, University of Pittsburgh , Pittsburgh, Pennsylvania 15260, United States.
authors.forename: Peng
authors.identifier: 0000-0002-8188-632X
authors.initials: P
authors.lastname: Liu
authors.affiliation: School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.|Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
authors.forename: Weiping
authors.identifier: 0000-0002-0039-3196
authors.initials: W
authors.lastname: Tang
mesh_terms: D000215:Acylation; D002241:Carbohydrates / Q000737:chemistry*; D002384:Catalysis; D002412:Cations / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013773:Tetramisole / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D002241:Carbohydrates; D002412:Cations; C515434:benzotetramisole; D013773:Tetramisole