Dicationic phosphonium salts: Lewis acid initiators for the Mukaiyama-aldol reaction

Abstract

Two strategies were used to prepare dicationic phosphonium cations. The first method consists of the reaction of 1-chlorocyclopropenium salts with phosphines to obtain cyclopropenium-substituted phosphonium salts 10a–f[BF₄]. Anion exchange was performed to access the corresponding [B(C₆F₅)₄]⁻ analogues 10a–f[B(C₆F₅)₄], which showed much higher solubility in organic solvents. In addition, we developed a synthesis of dicationic phosphonium salts containing 2-, 3-, or 4-methylpyridinium substituents 11a–c[TfO], which were converted as well to their [B(C₆F₅)₄]⁻ analogues 11a–c[B(C₆F₅)₄]. Finally, the phenoxy-substituted phosphonium salt 12[B(C₆F₅)₄] was also prepared. All salts demonstrated remarkable stability in air as compared with their fluorinated analogues. The Lewis acidity of these salts was evaluated by means of theoretical calculations and finally, they were shown to be effective in initiating the Mukaiyama-aldol reaction.