| Allylamines are significant building blocks for various bioactive compounds,which have wide existence in natural products and pharmaceuticals,such as allylamines antifungal drugs Naftifine,Terbinafine and Butenafine etc.In addition,the allylamine is transformed to a range of compounds by functionalization,reduction,or oxidation of the double bond,and allylamines have been widely used as starting materials for the synthesis of numerous biologically active compounds such asα-andβ-amino acids and different alkaloids.Therefore,the synthesis of allylamines has become a hot topic.The first chapter introduces the development of electrophilic reagents and nucleophiles for the palladium-catalyzed allylic substitution.The second chapter is palladium-catalyzed direct amination of allylic alcohols,among many types of synthetic methods available for constructing the allylamine scaffold,the transition-metal-catalyzed amination of allylic alcohols has proven to be one of the most efficient approach for the synthesis of allylamines,due to the high atom economy(water was produced as the only by-product)and step economy.The allylic amination require activated allylic alcohol derivatives(allylic halogens,acetates,carbonates,phosphonates etc),it will produce amounts of chemical wastes in both the preactivation and allylic amination steps and pollute the environment.The direct use of unactivated allylic alcohols would minimizes the step,the only byproduct is water,avoid the produce of the extra chemical wastes.The poor leaving ability of the OH group causes the substitutions of allylic alcohols to require activator of protic or lewis acids,use of special ligands,strictly anhydrous conditions or high temperatures.We make use of the hydrogen bond between protic solvent and allylic alcohols to make the direct allylic amination of allylic alcohols proceed without activators and needless of strictly anhydrous conditions at 30 ~oC,thus provide a new methods for activation of allylic alcohols. |
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