In this article, for the first time, we describe that commercially available and environmentally benign amine-functional polysiloxanes (AFPs) could be used as highly efficient metal-free amino catalysts in multicomponent Gewald reactions, α-allylic alkylations of aldehydes, and Knoevenagel condensations. Using catalytic amounts of AFPs, these transformations, including the Gewald reactions of ketones, sulfur, and ethyl 2-cyanoacetate, α-allylic alkylations of aldehydes and Knoevenagel condensations of aldehydes and the methylene-activated substrates may be carried out under mild conditions to give corresponding products in good yields.
    
         
            
                     
                    
                        
                            
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