The Synthesis Of (E)-α-Stannylvinyl Sulfones And Their Applications In High Selective Synthetic Reactions

This dissertation describles the stereoselective synthesis of 1,1-difunctional group reagents---- (E)-α- stannylvinyl sulfones and their applications in high selective synthetic reactions.The palladium-catalyzed hydrostannylation of acetylenic sulfones with tributyltin hydride gives versatile (E)-α-stannylvinyl sulfones which are new difunctional group reagents. Based on the reactivityes difference of tributylstannyl and sulfonyl groups, we carried out the cross-coupling reaction of (E)-α-stannylvinyl sulfones with alkenyl halides in the presence of Pd(PPh₃)₄/CuI, to afford the correponding 1,3-dienyl sulfones in high yields. We studied on the reactions of (E)-α-stannylvinyl sulfones with aryl iodide in the presence of Pd(PPh₃)₄/CuI, to afford the corresponding (Z)-1,2- disubstituted alkenylsulfones in high yields. We carried out the cross-coupling reaction of (E)-α-stannylvinyl sulfones with acetylenic bromides in the presence of Pd(PPh3)4/CuI, to afford the corresponding 1,3-enynylsulfones in high yields. (E)-α-Stannylvinyl sulfones underwent palladium-catalyzed coupling reaction with allylic bromides to give 1,4-dienylsulfones in good yields. We also investigated the tandem hydrostannylation-stille reaction of acetylenic sulfones with tributyltin hydride and alkenyl halides or allylic bromides , providing one pot stereoselective synthesis of 1,3-dienylsulfones or 1,4-dienylsulfones.