2.2 Arylation via a Smiles rearrangement
19
Figure 21: Nucleophilic -oxygenation of different amides.
This method complements our group’s reported -oxidation of amides.
[29]
In the course of our study, we noticed that even weakly nucleophilic DMF
could add to the enolonium species. If no other nucleophile, is present a suspension
of NaH in DMF reacted with the enolonium ion to form intermediate A which
upon aqueous work up gave formate 2.2o in 26% yield and alcohol 2.2p in 42%
(Figure 22). The same reaction carried out with dimethylacetamide instead of
DMF did not produce the -acetylated compound.
Figure 22: Attack of DMF on the enolonium intermediate.
2.2 Arylation via a Smiles rearrangement
With a range of -sulfonamido amides in hand we were eager to try a Smiles rearrangement as described above in chapter 1.3. This would lead to deprotected and
densely functionalised -amino--aryl amides.
19
Figure 21: Nucleophilic -oxygenation of different amides.
This method complements our group’s reported -oxidation of amides.
[29]
In the course of our study, we noticed that even weakly nucleophilic DMF
could add to the enolonium species. If no other nucleophile, is present a suspension
of NaH in DMF reacted with the enolonium ion to form intermediate A which
upon aqueous work up gave formate 2.2o in 26% yield and alcohol 2.2p in 42%
(Figure 22). The same reaction carried out with dimethylacetamide instead of
DMF did not produce the -acetylated compound.
Figure 22: Attack of DMF on the enolonium intermediate.
2.2 Arylation via a Smiles rearrangement
With a range of -sulfonamido amides in hand we were eager to try a Smiles rearrangement as described above in chapter 1.3. This would lead to deprotected and
densely functionalised -amino--aryl amides.