Computer-assisted mechanistic evaluation of oxidation reactions of organic compounds

The scope and predictive capability of the CAMEO (Computer Assisted Mechanistic Evaluation of Organic Reactions) program have recently been enhanced to encompass the chemistry of 21 oxidative reagents including transition metal acetates, metal and non-metal oxides, hydrogen peroxides and peracids, chromium (VI) oxidants, and other miscellaneous reagents. The implementation of the oxidation module required a new strategy which deviates from the purely standard mechanistic approach employed by the other modules in CAMEO owing to the dearth of existing mechanistic information on various oxidative transformations. An alternative method which utilizes reaction conditions and keys reactivity on the nature of the reagent has been adopted for the module. A general procedure consisting of four basic steps has been implemented in the program: (1) perception or identification of potentially reactive sites; (2) ranking of the sites based on relative reactivity; (3) weeding out of unreactive sites based on input reaction conditions; and (4) evaluation of competing pathways, if necessary, and storage of the required manipulations for the formation of products. Reactivity tables for all the reagents covered have been devised to help assess competitions among viable reactive sites. Efficient algorithms for evaluating multi-pathway transformations for a specific site have also been developed based on new reaction schemes that can account for all the observed transformations