Affiliation:
1. School of Chemical Sciences and Maurice Wilkins Centre for Molecular Biodiscovery The University of Auckland 23 Symonds St Auckland 1010 New Zealand
2. School of Chemical & Physical Sciences Victoria University of Wellington Kelburn Parade Wellington 6012 New Zealand
Abstract
AbstractAzide‐enolate cycloaddition‐rearrangements offer potential for rapid access to diverse molecular frameworks from simple precursors. We report here that investigations into the cycloadditions of ester or amide enolates with vinyl azides led to the identification of two reaction processes – direct α‐amination of amides and lactams, and the synthesis of ene‐γ‐lactams from esters. The outcomes of these reactions depended on the fate of key vinyl triazoline intermediates generated in the initial cycloaddition step. Isolation of reaction intermediates in the ene‐γ‐lactam synthesis revealed the unexpected addition of two enolate equivalents, one of which is later eliminated. Computational studies further suggested an unusual reaction pathway involving direct addition of an enolate to the terminal carbon of the N‐vinyl triazoline. In contrast, the α‐amination of amides and lactams proceeded by rearrangement of the intermediate triazoline to give an imine, hydrolysis or reduction of which gave access to primary or secondary α‐amino amides or lactams.
Subject
General Chemistry,Catalysis,Organic Chemistry
Cited by
1 articles.
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