O-Arylative Passerini Reactions

Abstract

The three-component addition of isocyanides to phenol derivatives and aldehydes proceeds easily in methanol to form O-arylated compounds in a new Passerini-type reaction. The key step of the conversion lies in an irreversible Smiles rearrangement of intermediate phenoxyimidate adducts. It represents the first use of a Smiles rearrangement in a Passerini reaction.

Radical Smiles Rearrangement: An Update

“…The Smiles rearrangement has recently appeared in multi-component reactions or one-pot approaches [10][11][12], but only a few reports of domino strategies involving this rearrangement are available, especially in a radical manner [13][14][15][16].…”

Smiles Rearrangements

“…[51][52][53] In this process, the coupling of an aldehyde, an amine, an isocyanide, and an electron-deficient phenol in a 1 M solution of methanol or toluene at 60 observed with a cyano or a phosphonate group. [51][52][53] In this process, the coupling of an aldehyde, an amine, an isocyanide, and an electron-deficient phenol in a 1 M solution of methanol or toluene at 60 observed with a cyano or a phosphonate group.…”

Benzoxazinone synthesis via Passerini–Smiles couplings

“…Our initial conditions for the Passerini-Smiles reaction suffered from a lack of reproducibility and a quite limited scope. 10 After examining the effect of various additives, we reported new conditions for the coupling and applied them to a straightforward access to 2H-benz[b] [1,4]oxazin-3(4H)-ones via a Passerini-Smiles/Smiles sequence (Scheme 1). 21 Considering the biological relevance of benzoxazinone scaffolds [22][23][24][25][26][27] and the efficient formation of O-aryloxy carboxamides 1, we decided to explore the reduction of the nitro group as an alternative Passerini-Smiles pathway to reach benzoxazinones (Scheme 1).…”