Nucleophilic nitrenoids

Nucleophilic nitrenoids are N-centred reagents that donate electron density to an electrophile, and then subsequently lose a leaving group, behaving as nitrene equivalents over a reaction. We have been exploring their use in gold-catalysed reactions to develop efficient new methods for nitrogen heterocycle synthesis.

We proposed that a nucleophilic nitrenoid could be used to deliver a new entry into cycloadditions, by reacting to generate a metal carbene from a pi-acid activated alkyne and delivering the means to quench it. In 2011 we reported the first example of this type of process. Since then, related approaches have been used in a wider variety of transformations.

For an early review of this area, see Miguel’s invited review in the Asian Journal of Organic Chemistry.

We are currently looking at expanding the potential of this approach and applying these methods to target synthesis.

These reactions are readily performed on gram scale
New N,N-dipole equivalents for annulations
The reaction shows good tolerance for structural and functional variety
Non-aromatic and functionalised systems can also be used
New nitrenoids as 1,3-N,N-dipole equivalents for annulations