Palladium Or Copper(Ⅱ)-Catalyzed Direct Sulfonylation Of C-H Bonds And Amino Or Oxy-Acetoxylation Of Alkenes

Sulfones are an important class of structural moieties found in pharmaceuticals and advanced materials. Moreover, sulfones could act as useful precursors for C-C bond formation via fragment coupling and Julia olefination in synthetic chemistry. Consequently, the synthesis of sulfones has attracted more and more attention. Recently, direct sulfonylation of C-H bonds cast a new vision for sulfones synthesis from the viewpoint of step- and atom-economy. However, these reactions are only scoped to palladium or ruthenium-catalyzed C(sp2)-H bonds sulfonyaltion. Thus, developing cheap metal such as Cu-catalyzed C(sp2)-H bonds sulfonylation and palladium-catalyzed C(sp3)-H bonds sulfonylation is more beneficial.Vicinal difunctionalization of alkenes represents as a powerful tool in the field of organic synthesis. Recently, great efforts have been devoted to the transition-metal-catalyzed vicinal difunctionalization of alkenes and made great progress in the last decade. However, there are still few examples of difunctionalization of alkenes for the synthesis of cyclic ureas and isoureas, and those reaction conditions are not mild. Thus, developing novel difunctionalization of alkenes for the synthesis of cyclic ureas and isoureas is desirable.This dissertation is mainly focused on palladium, copper-catalyzed direct sulfonylation of C-H bonds with sodium sulfinates and palladium, copper as the catalyst-controlled amino-versus oxy-acetoxylation of urea-tethered alkenes, which includes:1. Copper(Ⅱ)-Catalyzed Direct Sulfonylation of C(sp2)-H bonds with Sodium SulfinatesA copper-catalyzed direct sulfonylation of C(sp2)-H bonds with sodium sulfinates using a removable directing group is described. This reaction tolerates a wide range of functional groups, providing an efficient protocol for the synthesis of diverse aryl sulfones. Moreover, a series of 2,6-disubstituted benzamides could be synthesized via sequential C-H functionalization.2. Pd(Ⅱ)-Catalyzed Direct Sulfonylation of Unactivated C(sp3)-H Bonds with Sodium SulfinatesA Pd(Ⅱ)-catalyzed sulfonylation of unactivated C(sp3)-H bonds with sodium arylsulfinates using an 8-aminoquinoline auxiliary is described. This reaction demonstrates excellent functional group tolerance with respect to both the caboxamide starting material and the sodium arylsulfinate coupling partner, affording a broad range of aryl alkyl sulfones. Moreover, the late-stage modification of complex molecules was achieved via this sulfonylation protocol.3. Catalyst-Controlled Amino-Versus Oxy-Acetoxylation of Urea-Tethered AlkenesA catalyst-controlled vicinal amino-versus oxyacetoxylation of alkenes with PhI(OAc)2 as the oxidant is described. The divergent synthesis of cyclic ureas and isoureas was achieved in good yields under mild conditions employing ambident urea nucleophiles. Both terminal and internal alkenes are compatible with this reaction protocol.