Linear Free-Energy Relationship and Rate Study on a Silylation-Based Kinetic Resolution: Mechanistic Insights

RK Akhani, MI Moore, JG Pribyl…

Index: Akhani, Ravish K.; Moore, Maggie I.; Pribyl, Julia G.; Wiskur, Sheryl L. Journal of Organic Chemistry, 2014 , vol. 79, # 6 p. 2384 - 2396

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Citation Number: 11

Abstract

The substituent effect of different p-substituted triphenylsilyl chlorides on silylation-based kinetic resolutions was explored. Electron-donating groups slow down the reaction rate and improve the selectivity, while electron-withdrawing groups increase the reaction rate and decrease the selectivity. Linear free-energy relationships were found correlating both selectivity factors and initial rates to the σpara Hammett parameters. A weak correlation of ...