通过极化转移实现灵敏且准确的C动力学同位素效应测量。
Sensitive and Accurate C Kinetic Isotope Effect Measurements Enabled by Polarization Transfer.
作者信息
Kwan Eugene E, Park Yongho, Besser Harrison A, Anderson Thayer L, Jacobsen Eric N
机构信息
Department of Chemistry and Chemical Biology, Harvard University , Cambridge, Massachusetts 02138, United States.
出版信息
J Am Chem Soc. 2017 Jan 11;139(1):43-46. doi: 10.1021/jacs.6b10621. Epub 2016 Dec 29.
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.
摘要
极化转移被证明是一种用于测量天然丰度下质子化碳的同位素分馏的灵敏技术。与传统实验相比，该方法能够用少得多的材料或更短的采集时间来确定动力学同位素效应（KIEs）。计算定量地重现了狄尔斯-阿尔德反应和催化糖基化反应中的KIEs。结果表明，糖基化反应是通过一种有效的协同机制发生的。
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2
Transition state analysis of enantioselective Brønsted base catalysis by chiral cyclopropenimines.手性环丙烯亚胺对映选择性布朗斯特碱催化的过渡态分析
J Am Chem Soc. 2014 Jul 30;136(30):10700-7. doi: 10.1021/ja504532d. Epub 2014 Jul 16.
3
A general approach to mechanism in multiproduct reactions: product-specific intermolecular kinetic isotope effects.多产物反应中的机理的一般方法：产物特异性的分子间动力学同位素效应。
J Am Chem Soc. 2014 Apr 23;136(16):5832-5. doi: 10.1021/ja412827c. Epub 2014 Apr 10.
4
Highly precise measurement of kinetic isotope effects using 1H-detected 2D [13C,1H]-HSQC NMR spectroscopy.使用 1H 检测的 2D [13C,1H]-HSQC NMR 光谱技术进行高精准度的动力学同位素效应测量。
J Am Chem Soc. 2012 Dec 26;134(51):20589-92. doi: 10.1021/ja310353c. Epub 2012 Dec 11.
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6
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8
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9
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