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Sensitive and Accurate 13C Kinetic Isotope Effect Measurements Enabled by Polarization Transfer
Author(s) -
Eugene E. Kwan,
Yongho Park,
Harrison A. Besser,
Thayer L. Anderson,
Eric N. Jacobsen
Publication year - 2016
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.6b10621
Subject(s) - chemistry , kinetic isotope effect , isotope , kinetic energy , protonation , polarization (electrochemistry) , fractionation , isotope fractionation , glycosylation , catalysis , computational chemistry , chemical physics , deuterium , chromatography , organic chemistry , atomic physics , nuclear physics , ion , biochemistry , physics , quantum mechanics
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.

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