Computational Studies of Pericyclic Reactions between Aminoalanes and Ethyne, Ethene, and Dienes. A Reactive Aminoalane That Should Prefer [2+2] and [4+2] Cyclizations to Dimerization

摘要

The cyclic aminoalane 1 combines a nearly coplanar core with an endothermic dimerization energy, making it a candidate for computational studies of the chemical importance of the A1N pi interaction in pericyclic reactions between aminoalanes and alkenes/dienes. Reaction energy data indicate that 1 should undergo [2 + 2] cycloaddition as readily as or more readily than [4 + 2] cycloaddition, such that treatment of 1 with butadiene might provide multiple, bicyclic isomers. However, cyclization between 1 and 1,2-dimethylenecyclopentane should form only distal and proximal isomers. The overall reactivity of 1 indicates that the A1N pi interaction plays essentially no role in the chemical behavior of aminoalanes.