Nucleophilic Addition Reactions Of Acylsilanes

Acylsilanes have similar properties to aldehydes and unique physical and chemical properties.Although the reactivity is low,the compounds can undergo nucleophilic addition reactions with strong base or nucleophile.However,there are few reports on the nucleophilic addition reaction of acylsilane under mild reaction conditions.Therefore,it is still a challenge to achieve the nucleophilic addition reaction of acylsilane and nucleophile under simple and mild conditions.The main content of this paper is to achieve the nucleophilic addition reaction of acylsilane under simple and mild reaction conditions with different types of catalytic modes.The details are as follows:1.The decarboxylation and nucleophilic addition reaction of carboxylic acid and acylsilane is realized by bifunctional thiourea catalyst.The reaction products can be regulated by the catalysts:Brook rearrangement products are obtained when DBU is used as the catalyst;and decarboxylation-addition reactions can be obtained under the action of bifunctional thiourea catalysts.The method has mild conditions,simple operation and good broad reaction substrate.2.The nucleophilic addition reaction of dicyanoolefin and acylsilane under water phase conditions was achieved by DABCO.The research has shown that nucleophilic addition products can be obtained in the aqueous phase.In the organic phase,however,the product is rapidly decomposed by the catalyst of DABCO.The mechanism shows that the hydrogen bonding in water plays a decisive role in this type of nucleophilic addition reaction.Based on this reaction phenomenon,the concept of“On Water”relay chemistry was proposed.3.Under the aqueous zinc chloride solution,the Prins reaction of acylsilane andα-methyl olefin was successfully achieved.It is found that the molar ratio of water and ZnCl₂ plays an important role in adjusting the acidity.And the best results were observed when the molar ratio of anhydrous zinc chloride to water was fixed at 3:1.