Organophosphorus compounds are becoming increasingly useful in many applications such as industrial, agricultural and medicinal chemistry. In particular α-aminophosphonic acids and esters are structurally analogous to peptidomimetic compounds possessing diverse biological activities such as enzyme inhibition and antibiotic activities.<br/>A number of methods have been developed for the synthesis of α-aminophosphonates. Lewis acid or transition metal catalysts containing [Rh], [Co] and others have recently attracted much attention. However, those methods require harsh reaction conditions and use of toxic metal catalysts.<br/>To improve these methods, we envisioned the use of arynes as a part of a new synthetic pathway. In this work, we have developed a multicomponent phosponylation reaction without using metal-based reagents, which is a three-component coupling system involving arynes, imines and dialkyl phosphites. This method provides a more efficient and mild procedure applicable to various substrates, which obviates the use of transition metal-based reagents. A plausible mechanism is as follows: an iminium zwitterion, generated from a nucleophilic addition of an imine to an aryne abstracts a proton from a dialkyl phosphite in the reaction. Then the phosphite anion adds to the iminium ion to form α-aminophosphonates. Also, we have found an evidence for the nucleophilic addition of a deprotonated phosphite to an iminium intermediate using a deuterium isotope study.

Aryne-mediated phosphonylation of imines with dialkyl phosphites

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.