Study On Tin Powder Promoted Synthesis Of Ethyl α-Methylene-γ-Amino Carboxylate

Stannanes reagents is one of the most important organometallic reagents, which have been widely applied in organic synthesis due to their stability to oxygen and moisture, broad functional-group compatibility and high chemical selectivity. Recently, because the importance of environmental protection was more and more realized, the stannanes exposed some limitation in application of organic synthesis. For example, they are toxic and volatile, environmental pollution and low atom efficiency.Our group devoted to the development organic reaction mediated by tin powder. The method has the following advantages: catalyst free, atom economy and environmental benign.This thesis consists of the following three chapte rs:Chapter one: The research progress of stannanes in the organic synthesisThis chapter presents the application of stannanes in organic synthesis:(1) Stille cross-couplings reaction of stannanes reagents with aryl halides;(2) Bu3SnH- mediated radical reactions;(3) Allylation reaction of carbonyl compounds with allylstannanes;(4) Allylation reaction of imines and their derivatives with allylstannanes;(5) Tin powder mediated Barbier-type allylation reaction.Chapter two: Synthesis of ethyl α-methylene-γ-amino carboxylates promoted by tin powde rIn this chapter, we synthesized various of ethyl α- methylene-γ-amino carboxylates by treating aldehydes, aryl amines and ethyl 2-(bromomethyl)acrylate with tin powder at room temperature in 1,4-dioxane. The method is highly efficient and environmentally benign with catalyst- free, low cost and concise manipulation.Chapter three: Study on tin powder mediated enantioselective allylation of chiral hydrazidesChiral homoallylic amines are important building blocks for the construction of various biologically active compounds and natural products. In this chapter, we hope develop a tin- mediated highly enantioselective allylation of chiral hydrazides for the preparation chiral homoallylic amine compounds. We carried on the preliminary exploration of three-component allylation of aldehyde, allyl bromide and chiral hydrazides. Further investigation of reaction are currently underway.