The Spectroscopic Detection of Tetrahedral Intermediates Derived from Carboxylic Acids and the Investigation of Their Properties

Abstract

Publisher Summary This chapter explores that until a few years ago there was only indirect evidence for the existence of the species postulated as tetrahedral intermediates in reactions of derivatives of carboxylic acids. Now it is possible to generate some of them in solution at sufficiently high concentrations for their uv and nmr spectra to be measured and for their reactions to be studied. The aim of this chapter is to record progress that has been made in this area. The chapter reviews that indirect evidence for the incursion of tetrahedral intermediates in acyl-transfer reactions has been obtained from experiments, which indicate a change in rate-determining step and the incursion of an intermediate and from experiments that demonstrate a change in reaction products with pH that has been interpreted as resulting from a change in the partitioning of a tetrahedral intermediate. This large accumulation of indirect evidence clearly demonstrated the presence of tetrahedral intermediates in acyl-transfer reactions but virtually nothing was known about their chemical and physical properties.