Hydroxide Ion Initiated Reactions Under Phase Transfer Catalysis Conditions: Mechanism and Implications. New Synthetic Methods (62)

The development of Phase Transfer Catalysis (PTC) represents a major step forward in the employment of many organic reactions and renders them very convenient and useful processes. These reactions involve the application of nucleophiles in general, anions and bases in particular, in reactions carried out in a water‐organic solvent system. They can be performed both in the laboratory and on an industrial scale. The ease of application of PTC processes is the main reason for their increasing utilization in industry. An outstanding achievement of this technique is the employment of aqueous bases in reactions which traditionally would otherwise require a strong base in a nonaqueous medium. The classical procedures that require severe anhydrous conditions, expensive solvents and dangerous bases such as metal hydrides and organometallic reagents are now replaced by aqueous solutions of, e.g., sodium or potassium hydroxides (PTC/OH processes). In contrast to the extensive synthetic applications of PTC/OH systems, the detailed mechanisms of these processes have been the subject of a great deal of controversy and various mechanisms have been suggested. However, it would seem that our knowledge concerning the mechanistic aspects of such reactions has now reached the stage where it can be used to advantage in synthesis planning. A better understanding of the various factors which influence the reaction would undoubtedly help to optimize PTC/OH processes such as to enable higher yields in shorter reaction times at lower temperatures. The importance of, inter alia, the catalyst will be pointed out and it is highly recommended that such catalysts be always available in the laboratory, for the range of organic reactions that they can efficiently, conveniently and safely catalyze is vast indeed. Severe anhydrous conditions, expensive solvents and dangerous bases can often be dispensed with if classical methods are replaced by phase‐transfer processes which involve the use of aqueous solutions of NaOH or KOH (PTC/OH processes). Decisive is the catalyst: not only have quaternary ammonium and phosphonium ions proven especially suitable in this respect, but also crown ethers, cryptates, and open‐chain polyethers. Even though the mechanisms are controversial, valuable new ideas can be stimulated for the optimization of PTC/OH processes.