Olefin reaction with organic halides

Palladium-catalyzed coupling reactions of organic halides with olefins or dienes (R. F. Heck, 1979) are broad in scope and simple to carry out. Anhydrous conditions or any special technique are not required and most functional groups are tolerated. 

Transition Metal-Catalyzed Reactions of Organic Halides with CO, Olefins, and Acetylenes R. F. Heck... 

Numerous metal-catalyzed reactions of organic halides with carbon monoxide and olefins, acetylenes, aldehydes, etc., have been carried out (21). Only two of these, however, appear to have been developed into generally useful reactions. One is the reaction of allylic halides with carbon monoxide and acetylene in alcoholic solution with a nickel catalyst (22,23). This reaction produces cis-2,5-hexadienoate esters at atmospheric pressure in good yields ... 

Heck RF (1979) Palladium-catalyzed reactions of organic halides with olefins. Acc Chem Res 12 146-151... 

Heck RF. Transition metal-catalyzed reactions of organic halides with carbon monoxide, olefins, and acetylenes. Adv. Catal. 1977 26 323-349. 

In the reaction, an organic halide first forms an organopalladium halide complex with the catalyst, by oxidative addition. This complex then adds to an olefin and the adduct decomposes, by elimination of a hydrido-palladium halide, to form a new olefin in which a vinylic position is substituted by the organic moiety of the substrate halide. 

The cross-coupling reaction of organic halides or their equivalents with either olefins or organometallic nucleophiles belongs to the standard repertoire of the organic chemist. It is almost without exception catalyzed by palladium complexes. Little new mechanistic evidence has appeared, and the reaction appears now to be well understood. The following references represent a very small selection from the publications on this topic and were chosen since they address some less-usual aspects. 

Sustmann, R., Hopp, P. and HoU, P. (1989) Reactions of organic halides with olefins under Ni(0)-catalysis. Formal addition of hydrocarbons to CC-double bonds. Tetrahedron Lett., 30, 689-92. 

In reactions with organic molecules e q reacts as nucleophilic reagent it attacks molecules with low-lying molecular orbital, like aromatic hydrocarbons, conjugated olefinic molecules, carboxyl compounds, and halogenated hydrocarbons (Swallow 1982 Buxton 1982, 1987 Buxton et al. 1988). In the latter case, addition is usually followed by halide ion elimination, so the reaction can be considered as a dissociative electron capture. For instance, the reaction with chlorobenzene yields phenyl radical and chloride ion... 

The same authors also used ESI-MS/MS to study an air-promoted oxidative Heck reaction between arylboronic acids and enamides as electron-rich olefins (Scheme 7.13) [29]. In addition to the conventional Mizoroki-Heck reaction of unsaturated compounds with organic halides or triflates as electrophiles, the use of nucleophilic organometallic reagents, such as organoboron compounds, has... 

R. E. Heck, Acc. Chem. Res., 1979, 12, 146-151. Palladium-Catalyzed Reactions of Organic Halides with Olefins. 

Nickel-catalyzed electroreductive homocoupling reaction of organic hahdes and coupling reaction between organic halide and activated olefins could be carried out with iron anode in ionic liquid. With addition of small amount of DMF, coupling compounds were obtained at room temperature in good to high... 

The Nickel Triad,—The tetranuclear complex [ Ni2(CO)20 -C3Cl3XiM-Cl) 2] (36), formed from nickel tetracarbonyl and tetrachlorocyclopropene, contains ring-opened trichloropropenyl ligands bridging bonded pairs of nickel atoms. The complexes [NiPh(acac)(PR3)] react with organic halides (R X) to form cross-coupled products (Ph-R ), and undergo insertion and jS-elimination reactions with olefins to yield phenyl substituted organic products. The methyl complexes... 

SF5CF=CF2 and SF5CH=CF2 (60,61). The chief advantage of the phosphonium salts lies in their convertibility to the iodide -F5SCF=CFI. The iodide should be useful for the synthesis of SF5-substituted butane derivatives by photochemical addition of olefins, or perhaps by generating a metal organic intermediate followed by reaction with alkyl halides. 

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