Transition-metal-free α-arylation of carbonyl compounds via Smiles Rearrangement

Abstract

The Smiles rearrangement, a valuable synthetic tool for constructing complex molecular architectures, has been extensively employed in organic synthesis. In recent years, there has been increased interest in applying the Smiles rearrangement to the arylation of α-carbonyl compounds. We developed a transition metal free alpha arylation of carbonyl compounds via Smiles Rearrangement under mild reaction conditions using: 1- Sulfonates 2- Sulfonamide The use of sulfonates as arylating reagents presents certain limitations, and further investigation is required to improve the efficiency of the rearrangement, which could enhance the overall synthetic pathway. Conversely, sulfonamides have demonstrated potential as effective arylating agents for producing complex molecules under mild conditions. Further exploration is necessary to broaden the scope and optimize conditions to achieve better yields and selectivity. Efforts to achieve asymmetric synthesis of Smiles products from sulfonates were undertaken, but these attempts faced significant challenges, particularly in attaining satisfactory enantioselectivity with the current methodology.