Source of Intramolecular and Enzymatic Reactivity

摘要

Intramolecular reactions often proceed much faster than their intermolecular counterparts. The source of the acceleration (often several powers of ten in magnitude) is not well understood. An effective molarity (EM) parameter has been devised to quantify intramolecularity. EM is defined as k sub intra/k sub inter operating under identical mechanisms. The present Account focuses on one central question: Why are certain intramolecular reactions characterized by extremely large EM values. Experimental and theoretical data of our own will be coupled with work of others in an attempt to answer this question.