| This paper study the synthesis of ferrocenyl sulfone,ferrocenyl pyridine and ortho-aromatic heterocycles substituted ferrocenyl azine compounds using ferrocenyl N-tosylhydrazone as raw material.And it is divided into three parts.In the first part,the reaction of Cu-catalyzted ferrocenyl N-tosylhydrazone is studied.After the selection of catalyst,base,solvent,the optimized conditions were obtained as following:CuI（20 mol%）,K2CO3（3.0 equiv.）in dioxane at 110 oC under Nitrogen for 14 h.And we have synthesized a series of ferrocenyl sulfone compounds with high yields（69-92%）through intramolecular reaction using optimized conditions.At the same time,we increased the amount of catalyst and base,and received 1,1’-disubstituted ferrocenyl sulfone.In addition,the ferrocenyl N-tosylhydrazones are always used as alkylation reagent.And based on that,we designed the second part.With optimized conditions in hand:pyridine N-oxides（1.0 equiv.）,ferrocenyl N-tosylhydrazone（2.0 equiv.）,CuI（20 mol%）,LiOtBu（3.5 equiv.）in dioxane at 100 oC under Nitrogen for 12 h,we synthesized ferrocenyl pyridine N-oxides in moderate yields（27-72%）and high selectivity via Cu-catalyzted couping reaction of ferrocenyl N-tosylhydrazone with pyridine N-oxides as the substrates.Then,we conducted a reduction experiment on the 4a and obtained the deoxygenated product 4p.In the third part,a Pd-catalyzed,cross-coupling reaction between ferrocenyl azine and heteroarenes is described.In this case,azine group act as a directing group,ortho-benzofuran-substituted ferrocenyl azine is synthesized via double C-H bond activation.The reaction conforms to the principle of atomic economy.Later,we studied the universality of the reaction and obtained a range of ortho-aromatic heterocycle substituted ferrocenyl azines with moderate to low yields（32-43%）.They may be used for the preparation of planar chiral ferrocene derivatives in the future.In addition,all products are characterized by 1H NMR,13C NMR and HRMS. |
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