title: Sensitive and Accurate13C Kinetic Isotope Effect Measurements Enabled by Polarization Transfer.
abstract: Polarization transfer is demonstrated as a sensitive technique for the measurement of isotopic fractionation of protonated carbons at natural abundance. This method allows kinetic isotope effects (KIEs) to be determined with substantially less material or shorter acquisition time compared with traditional experiments. Computations quantitatively reproduce the KIEs in a Diels-Alder reaction and a catalytic glycosylation. The glycosylation is shown to occur by an effectively concerted mechanism.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
authors.forename: Eugene E
authors.initials: EE
authors.lastname: Kwan
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
authors.forename: Yongho
authors.initials: Y
authors.lastname: Park
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
authors.forename: Harrison A
authors.initials: HA
authors.lastname: Besser
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
authors.forename: Thayer L
authors.initials: TL
authors.lastname: Anderson
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
authors.forename: Eric N
authors.identifier: 0000-0001-7952-3661
authors.initials: EN
authors.lastname: Jacobsen
mesh_terms: D002247:Carbon Isotopes; D061565:Cycloaddition Reaction; D006031:Glycosylation; D007700:Kinetics; D011789:Quantum Theory
chemical_list: D002247:Carbon Isotopes