Iron Catalyzed Allylic Substitution, The Number Of Organic Reactions

Iron-catalyzed substitution reactions including nucleophilic substitution, electrophilic substitution and cross-coupling and so on, are various convient methods for forming new carbon-carbon bonds and carbon-nitrogen bonds, which has great significance to organic synthesis. With the development of modern organic synthetic chemistry, iron catalysis is consistent with "green chemistry" concept and has been developing rapidly, in comparison to the rare earth metals and other transition metal catalysts, Iron-catalyzed have potential academic and industrial values.This thesis focuses on iron-catalyzed allylic substitution reaction and other reactions.In this paper, we reviewed recent developments of iron catalyzed organic synthesis reactions, and then proposed thesis topic, and systemically investigated iron-catalyzed allylic substitution reaction and Michael-type Friedel-Crafts reaction.Firstly we used FeCl3 as catalyst and discovered for the first time iron-catalyzed Tsuji-Trost coupling of active methylene compounds especially acetylacetone with aromatic allylic amides, this paper examined allyl reagents, solvents and various substituents on the reaction. The proposed reaction mechanism may be formed carbocation intermediate. This is a successful example that iron-catalyzed cleavage of sp3 carbon-nitrogen bonds to form carbon-carbon bonds. Then the FeCl3 reagent for the participation of catalytic synthesis of organic silicon conversion reaction and found that the addition of acetyl acetone can greatly enhance the catalytic activity of iron, so we have set up a complex catalysts which cotain FeCl3 and acetyl acetone, is more effect than pure FeCl3 reagent.Then we explored iron-catalyzed Michael-type Friedel-Crafts reaction of indoles with aromatic ketones, afforded 3-functionalized indole derivatives. Moreover, LBAs-based mechanism is presented according to the results, in witch the LBAs-based mechanism of iron-catalyzed organic transformation is established by the utilities of ESI-MS and cyclic voltammogram. It is believable that a novel entry to detect useful metal ion based intermediate especially with cyclic voltammogram in homogeneous catalysis has been opened.In addition, in the thesis we synthesized a series of chiral diamine derivatives as organic catalysts, and then studied their catalytic properties in the Michael addition, which mep out the special catalytic activity of Ts-DPEN in the Michael addition with good diasteree and stereoselectivity.