Chapter Two - New Applications of Isotope Effects in the Determination of Organic Reaction Mechanisms

Abstract

Abstract Our understanding of the basic physical processes that govern chemical reactions has put us at the cusp of beginning to understand, in stark detail, the way in which reactivity and selectivity are determined in organic reactions. Recent efforts at new experimental design coupled with the advent of enabling technologies have created a target-rich environment for the physical organic chemist. Additionally, computational chemistry has continued to develop apace of experiment in a manner that has facilitated the integration of experimental and computational efforts in the study of reaction mechanism. Few endeavors demonstrate the synergy of experiment and theory more convincingly than the study of isotope effects. This review will begin by introducing isotope effects using both mathematical and conceptual constructs. The second major section of this review will cover recent experimental and computational advancements in isotope effect methodologies. The third section of this review will take a systems approach that will highlight areas of chemical and biochemical mechanism in which isotope effects are advancing those fields. Finally, this review will look forward to the major challenges in chemical mechanism and identify areas where isotope effects may be critical to achieving vertical advancements.