Palladium-Catalyzed Reactions of Vinylic Bromides with Allylic Alcohol and Amine Derivatives

Article abstract of DOI:10.1021/jo00346a023

Allylic alcohols, amines, tetrahydropyranyl ethers, N-allylphthalimide, and tetraallyl silicate have been reacted with various vinylic bromides and, in some cases, bromobenzene by using a palladium catalyst with an amine as an acid acceptor.Of the allylic alcohols, methallyl alcohol was the most useful synthetically.It produced 4-enals in modest yields in many examples without formation of the regioisomeres which are a problem in other cases.Secondary allylic alcohols reacted regioselectively to from mixtures of 4-enals and amino alcohols.Some nonallylic alcohols gave good yields of amino alcohols, also.Allylic tertiary amines reacted more selectively in some instances than allylic alcohols, producing 4-enals after hydrolysis of the enamine products.The allylic tetrahydropyranyl ethers, in general, formed mixtures of dienyl ethers and amino alkenyl ethers.The N-allylphthalimide-vinylic bromide reactions were the most selective we found.The products were N-(2,4-dienyl)phthalimides, formed in fair to good yields.The reactions of tetraallyl silicate were of limited value.The reaction was selective with bromobenzene, forming after hydrolysis only cinnamyl alcohol, but it was not selective with vinylic halides, and conversions were always low due to facile reduction and inactivation of the catalyst under the reaction conditions.