The Kinetics of Isomer-Specific Oxygen Exchange Reactions of Optically Active Alcohols

在化学学部有机动力学项目（“酸催化外消旋化作用下光学活性醇的异构体特异性氧交换反应动力学”）中，韦尔斯利学院化学系的Margaret V. Merritt教授将测定同分异构体氧交换速率常数作为一系列手性醇外消旋作用的函数。这些详细的动力学研究将加强对这些和相关体系中反应机理和反应中间体的理解。氧交换速率常数作为一系列手性醇外消旋化的函数，将用于探索导致碳阳离子中间体不对称溶剂化的结构特征，并研究溶剂化球内水的结构。机制结论将基于α碳原子上三个竞争过程的微观速率常数和这些过程的氧同位素效应。所研究的三种相互竞争的过程是：取代（O-18交换）无反转、取代（O-18交换）有保留和反转（O-18交换）无取代。

In this project ("The Kinetics of Isomer-Specific Oxygen Exchange Reactions of Optically Active Alcohols as a Function of Acid-Catalyzed Racemization") in the Organic Dynamics Program of the Chemistry Division, Professor Margaret V. Merritt of the Chemistry Department at Wellesley College will determine the rate constants for oxygen exchange for isomers as a function of racemization of a series of chiral alcohols. These detailed kinetic studies will enhance the understanding of reaction mechanisms and reaction intermediates in these and related systems. The rate constants for oxygen exchange as a function of racemization of a series of chiral alcohols will be used to probe the structural features that lead to asymmetric solvation of carbocation intermediates and to investigate the structure of water within the solvation sphere. The mechanistic conclusions will be based on the microscopic rate constants for three competing processes at the alpha carbon atom and the oxygen isotope effects for these processes. The three competing processes being studied are substitution (O-18 exchange) without inversion, substitution (O-18 exchange) with retention, and inversion without substitution.