Application of natural abundance 2H NMR. Simultaneous measurement of primary and secondary kinetic deuterium isotope effects

Internal and external reference methods are introduced for the study of kinetic deuterium isotope effects (KDIEs) by natural abundance 2H NMR. These methods take account of both inter‐ and intra‐molecular competive reactions of fully protonated and naturally monodeuteriated molecules of the substrate in the reaction. Specifically deuteriated compounds are not necessary using these methods. These techniques have further advantages over other methods; for example, primary and secondary KDIEs of different types can be measured simultaneously. The methodology is summarized and examples of its application are presented.