Mechanistic Investigation of Allylic Azides
Allylic azides have been known to undergo spontaneous rearrangement to form an equilibrating mixture of branched and linear azides. Although the mechanism for such an event has been speculated in the past, detailed investigations have not been done yet to elucidate key intermediates or favorable energetic pathways. Experimentally, it has been shown that substituents on the allylic azide can affect the reaction equilibrium and subsequently the ratio of the equilibrating mixture. This equilibrium may also be influenced by interactions like hydrogen bonding of the substrate, however no experimental evidence substantiates these claims.
Computational studies can go a long way in gaining mechanistic insights of these reactions by identifying favorable transition states and/or reactive intermediates and role of various non-covalent binding events. These researchers envision that mechanistic analysis of the allylic azide rearrangement will provide insights for optimization of current reaction conditions. With these insights, the allylic azides can be synthetically converted to value added precious materials like chiral amines, which are important moieties in various substances like drugs, natural products, and more.
Return to this PI's main page.