COMPUTER-ASSISTED MECHANISTIC EVALUATION OF ORGANIC-REACTIONS .23. DISSOLVING METAL REDUCTIONS WITH LITHIUM IN LIQUID-AMMONIA INCLUDING THEBIRCH REDUCTION

The computer program CAMEO, which predicts the products of organic rea ctions, has been expanded to treat reductions with lithium in liquid a mmonia. A comprehensive reactivity table controlling selectivity has b een amassed from literature precedents. Individual reactive sites in a n input substrate are evaluated using existing routines for calculatin g pK(a)s and bond dissociation energies. In the course of processing, charged mechanistic intermediates are explicitly created. When accompa nying intramolecular substitutions, additions, and eliminations may oc cur, the intermediates are automatically submitted to the Basic/Nucleo philic module of CAMEO for further processing. Reaction sequences in t he paper illustrate the current predictive capabilities of the program .