[3 + 2] Cycloadditions in Asymmetric Synthesis of Spirooxindole Hybrids Linked to Triazole and Ferrocene Units : X-ray Crystal Structure and MEDT Study of the Reaction Mechanism

Abstract

Derivatization of spirooxindole having triazole and ferrocene units was achieved by the [3 + 2] cycloaddition (32CA) reaction approach. Reacting the respective azomethine ylide (AY) intermediate generated in situ with the ethylene derivative produced novel asymmetric cycloadducts with four contiguous asymmetric carbons in an overall high chemical yield with excellent regioselectivity and diastereoselectivity. X-Ray single-crystal structure analyses revealed, with no doubt, the success of the synthesis of the target compounds. The 32CA reaction of AY 5b with ferrocene ethylene 1 has been studied within MEDT. This 32CA reaction proceeds via a two-stage one-step mechanism involving a high asynchronous transition state structure, resulting from the nucleophilic attack of AY 5b on the β-conjugated position of ferrocene ethylene 1. The supernucleophilic character of AY 5b and the strong electrophilic character of ferrocene ethylene 1 account for the high polar character of this 32CA reaction. Further, Hirshfeld analyses were used to describe the molecular packing of compounds 4b, 4e, 4h and 4i.