Study On Novel Reactions Of Aryl Allenylmethyl Ether Involving The Cleavage Of C-O Bond

Allenes contain two cumulative double bonds,which not only exist in natural products and drugs,but also serve as important organic building blocks.Naphthofuran derivatives are widely found in natural products and physiological active compounds,and also have valuable applications in organic semiconductor materials.Sulfonylhydrazones and sulfonamides are widely found in drug molecules.This work consists of three parts:synthesis of 2-aryl/alkyl-3-(substituted-vinyl)naphthofuran derivatives,synthesis of?-hydrazone allene derivatives and synthesis of?-sulfonamide allene derivatives.The first part is the synthesis of 2-aryl/alkyl-3-(substituted-vinyl)naphthofuran derivatives.2-Aryl/alkyl-3-(substituted-vinyl)naphthofuran derivatives were obtained from aryl allenylmethyl ethers in moderate to good yields with high chemo-,regioselectivity through Fe Cl₃ catalyzed Claisen rearrangement/intramolecular oxidative coupling with O₂ as terminal green oxidant in an atom and step economic fashion.The second part is the synthesis of?-hydrazone allene derivatives.Aryl allenylmethyl ethers and sulfonylhydrazones served as starting material with Pd₂(dba)₃ as catalyst and Xphos as ligand in THF,and a series of?-hydrazone allene derivatives were smoothly obtained in high yields under mild conditions.The third part is the synthesis of?-amino allene derivatives.Under catalytic amounts of Pd₂(dba)₃ and Xphos ligand,aryl allenylmethyl ethers reacted with sulfonamides to form the novel C-N bond through breaking C-O bond,and?-sulfonamide allene derivatives were obtained in moderate to excellent yields.The reaction was charactered by mild condition,short reaction time and broad substrate scope.