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

在化学部有机动力学程序中的这个项目(作为酸催化外消旋作用的光学活性醇异构体特定氧交换反应的动力学)中，卫尔斯理学院化学系的玛格丽特·V·梅里特教授将根据一系列手性醇的外消旋反应来确定异构体的氧交换速率常数。这些详细的动力学研究将加深对这些体系和相关体系中的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的函数将被用来探索导致碳正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。力学结论将基于三个相互竞争的过程在α碳原子处的微观速率常数和这些过程的氧同位素效应。被研究的三个相互竞争的过程是没有倒置的取代(O-18交换)、有保留的取代(O-18交换)和没有取代的倒置。

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.