Secondary Isotope Effects

I. Theory and Nomenclature ............................................................................................... 955

II. Origins of Secondary Isotope Effects .............................................................................. 956

A. Secondary Isotope Effects Resulting from Hybridization Changes........................ 956

B. Secondary Isotope Effects on Acidities................................................................... 959

C. Steric Secondary Isotope Effects ............................................................................. 960

III. Secondary Isotope Effects in Particular Reactions.......................................................... 961

A. Acyl Transfer ........................................................................................................... 961

B. Glycosyl Transfer..................................................................................................... 964

C. N-Ribosyl Hydrolases and Transferases .................................................................. 965

D. Phosphoryl Transfer ................................................................................................. 966

E. Methyl Transfer........................................................................................................ 968

F. Hydride Transfer ...................................................................................................... 969

G. Peptidyl Prolyl Cis-Trans Isomerase...................................................................... 969

References..................................................................................................................................... 975

There are a number of extensive discussions of the origins of secondary isotope effects in the

literature

and in this volume (see Chapter 1). For this reason, only the basic concepts will be

presented here, and interested readers are referred to these prior reviews for more in-depth

discussions.