Bacteria, fungi, and plants produce an arsenal of complex biomolecules through which they interact and compete with neighbor organisms (1). The machinery that builds these molecules is replete with iron(II)and 2-(oxo)glutarate-dependent (Fe/2OG) oxygenases, enzymes that catalyze hydroxylation, halogenation, desaturation, ring-closure, ringexpansion, and stereoinversion reactions on pathways to ...

A new stereoelectronic theory for the cleavage of the tetrahedral intermediate in the hydrolysis of esters and amides is presented. In this new theory, the precise conformation of the intermediate hemi-orthoester or hemi-orthoamide controls the nature of the hydrolysis products. It is postulated that the breakdown of a conformer of a tetrahedral intermediate depends upon the orientation of the ...