Mild and Efficient Aryl−Alkenyl Coupling via Pd(II) Catalysis in the Presence of Oxygen or Cu(II) Oxidants

Abstract

We report herein a mild and efficient method for carbon-carbon bond formation between aryl stannanes and olefins via Pd(II) catalysis in the presence of oxygen or Cu(II) oxidants as a reoxidant. The process allows reactions between various olefins and aryl stannanes of varying electron density. Coupling methods under these oxidation conditions are comparatively described, and the benefits and limitations are also discussed.

Palladium Oxidase Catalysis: Selective Oxidation of Organic Chemicals by Direct Dioxygen‐Coupled Turnover

“…Other aryl metal chlorides, including Ph 2 TlCl, Ph 3 SnCl, and Ph 2 TeCl 2 , were not successful in this reaction. Subsequently, Jung and co-workers described the use of aryl stannanes [66] in oxidative cross-coupling reactions with alkenes ( Table 2). These reaction conditions proved more versatile than those reported previously with copper(ii) salts as the oxidant.…”

C–C Cross‐Coupling Reactions of Organosilanes with Terminal Alkenes and Allylic Acetates Using PdII Catalyst Supported on Starch Coated Magnetic Nanoparticles

“…The pioneering route for constructing C–C bonds involves the cross‐coupling reactions using various organometallic and organometalloid reagents. Heck coupling and Tsuji–Trost coupling are two important tools for C–C bond formations leading to total synthesis of many natural products and biologically active organic compounds The oxidative Heck reaction has recently gained more attention mainly because of air and moisture insensitive reaction conditions using organoboron, organotin and organosilicon reagents as the coupling partners. Among common organometallic reagents organosilicon compounds are attractive due to their stability, low toxicity, low‐cost and high natural abundance of silicon .…”

Oxidative Heck Coupling Using Pd(II) Supported on Organosilane-Functionalized Silica Mesocellular Foam

“…First described by Heck in 1975 using a stoichiometric amount of palladium salts [2], the catalytic cycle was closed in the presence of a co-oxidant, usually a salt such as Cu(OAc) 2 [3] or molecular oxygen [4], to regenerate Pd(II) from Pd(0). The current diversity of accessible arylboronic acids, their relative stability in air and moisture, their low toxicity and the ease of boron-derived byproduct removal have made oxidative Heck coupling a popular building block organic reaction [4][5][6][7][8][9][10][11][12].…”