Regioselective Synthesis of Fused Oxazepinone Scaffolds through One-Pot Smiles Rearrangement Tandem Reaction

Abstract

The paper describes a convenient and facile methodology for the regioselective synthesis of fused oxazepinone scaffolds. This process is an efficient construction of the oxazepinone scaffold by a one-pot coupling/Smiles rearrangement/cyclization approach. This transition metal-free process has potential applications in the synthesis of biologically and medicinally relevant compounds.

Copper‐Catalyzed Cross‐Coupling Interrupted by an Opportunistic Smiles Rearrangement: An Efficient Domino Approach to Dibenzoxazepinones

“…Although Smiles rearrangements of diaryl ethers bearing secondary amides have been previously reported,14 the systems investigated typically involve arenes bearing multiple electron‐withdrawing groups (for example, NO 2 , CN, F) or strongly electron‐deficient heteroaromatic rings, such as pyridine 15. In stark contrast, our reaction progresses smoothly in the presence of both electron‐neutral and electron‐rich phenols.…”

Copper‐Catalyzed Cross‐Coupling Interrupted by an Opportunistic Smiles Rearrangement: An Efficient Domino Approach to Dibenzoxazepinones

“…Although Smiles rearrangements of diaryl ethers bearing secondary amides have been previously reported, [14] the systems investigated typically involve arenes bearing multiple electron-withdrawing groups (for example, NO 2 , CN, F) or strongly electron-deficient heteroaromatic rings, such as pyridine. [15] In stark contrast, our reaction progresses smoothly in the presence of both electron-neutral and electron-rich phenols. Perhaps most surprisingly, these substrates often outperform their electron-poor counterparts, which are less-tolerated.…”

Metal-Free Synthesis of Dibenzoxazepinones via a One-Pot SNAr and Smiles Rearrangement Process: Orthogonality with Copper-Catalyzed Cyclizations

“…Particularly good substrates are heavily halogenated phenols and electronically deficient heterocycles (Table 3, entries 4, 5, 8), which are known to be effective participants in Smiles rearrangement processes. [6][7][8][9][10]16 Substituents which modulate either the nucleophilicity of the phenol (Table 3, entry 6) or lessen the stability of the putative Meisenheimer intermediate 17 (Table 3, entries 1, 2, 7) decrease the efficiency of the reaction.…”