Studies On Palladium-Catalyzed Cascade Reactions Involving Diazo Compounds And Catellani-Lautens Reactions

Chapter ⅠIn part 1, we summarize the recent developments in palladium-catalyzed diazo compounds insertion reaction. According to the mechanism, these reactions can be categorized into two types:(1) Simple palladium-catalyzed diazo compounds cross-coupling reactions; (2) Palladium-catalyzed diazo compounds cascade reaction.In part 2, we summarize the most recent advances in Catellani-Lautens reaction. These reactions involve a Pd-catalyzed/norbornene-mediated C-H activation/terminal cross-coupling process. A series of nucleophilic coupling partners, which include alkene or alkyne, organometallic reagent, hydrogen transfer reagent and heteroaromatics compound, could be used in terminal cross-coupling process.Chapter ⅡTwo different cyclic amino esters are synthesized by palladium-catalyzed cascade reaction of diazoesters with N-benzyl-2-iodoanilines. Aryldiazoacetates lead to cyclic a-amino ester with a a-quaternary carbon centre. Additionally, arylvinyldiazoacetates afford cyclic α, β-unsaturated γ-amino esters.Chapter ⅢIsoindolines are synthesized by palladium-catalyzed cascade reaction of N-(2-iodobenzyl) anilines with α, β-unsaturated N-tosylhydrazones. The reaction has several potential advantages:(1) Toleration of a wide range of functional groups; (2) Easy to handle and with mild conditions; (3) Enriched the isoindoline family; (4) Two new bonds formed in one step.Chapter ⅣWithout extra addition sulfinate salt, allylic sulfones were synthesized by palladium-catalyzed cross coupling of aryl iodide with α, β-unsaturated N-tosylhydrazone. In this transformation, not only the diazo compound but also the sulfinate salt, which were both generate in situ from base-mediated decomposition of the N-tosylhydrazone, was used as nucleophilic partner.Chapter ⅤA Pd-catalyzed three-component cascade reaction of vinyl iodide, N-tosylhydrazone, and carbon nucleophiles is reported, and a one-pot procedure is also developed. This cascade reaction is proposed to proceed through a palladium carbene migratory insertion, carbopalladation other than classic palladium carbene migratory insertion and β-H elimination. Moreover, the reaction proceeds under mild conditions and with high stereoselectivity.Chapter ⅥA straightforward method for the synthesis of highly functionalized vinylarenes via palladium-catalyzed, norbornene-mediated C-H activation/carbene migratory insertion is described. Extension to one-pot procedure is also developed. Furthermore, this method can also be used to generate polysubstituted bicyclic molecules. The reaction proceeds under mild conditions to give the products in satisfactory yields using readily available starting materials. This is an unprecedented Catellani-Lautens reaction, in which incorporate a different types of coupling partners. Additionally, this reaction first demonstrates the possibility of combination Pd-catalyzed insertion of diazo compound and Pd-catalyzed C-H activation.Chapter ⅦOrtho-amination vinylarene derivatives are obtained via a reaction of aryl iodides, N-benzoyloxyamines and N-tosylhydrazones. This approach involves a palladium-catalyzed, norbornene-mediated ortho-amination/N-tosylhydrazone insertion reaction. In this transformation, one C-N bond and one C-C bond are formed and an amine group is introduced at the ortho-position successfully.Chapter ⅧA palladium-catalyzed selective C-H bond acylation of arene by carboxylic acid derivatives is reported. The reaction was carried out with readily available starting materials to give the ortho-acylated styrene in satisfactory yields. Compared to previous Catellani-Lautens reaction, this reaction is the first example of introduction an acyl groups at the ortho-position of aryl iodides.