Alkenes metal halide reaction with

Sulfenamides can be synthesized by a metal-assisted reaction with disulfides and amines (eq 13). Conjugated dienols can be synthesized in a highly chemo-, regio-, and stereoselective manner from vinylic halides and allylic alcohols (eq 14). Silver acetate (or silver carbonate) and a catalytic amount of palladium(II) acetate in DMF are the preferred conditions. The reaction is very attractive because it requires only one functionalized alkene reactant and the addition of the vinylic group only occurs at the terminal carbon of the aUyUc alcohol. 4... 

Reaction of a Metal Halide with an Alkene in a Nonaqueous Solvent... 

Reaction of a Gaseous Alkene with a Solution of a Metal Halide... 

RMn(CO)5.3 Alkylmanganese pentacarbonyl complexes are obtained by reaction of alkyl halides with NaMn(CO),. Under pressures of 2-10 kbar, these complexes undergo an insertion reaction with alkenes to give usually a single manganacycle in which the electron-withdrawing group of the alkene is attached to the same carbon atom as the metal. Demetallation is accomplished by photolysis... 

This paper was presented at the Symposium on Polymer Chemistry as Applied to Plastics on the 22nd of September 1950. In it the author recognises the possible types of reaction by which a co-catalyst may initiate polymerisation in a mixture of an alkene and a metal halide. It is stated, probably not for the first time, that the hydrogen halides, HX, do not form protonic acids with metal halides, but nonetheless these ghosts kept on spooking around the literature for decades, and they have still not been exorcised completely. 

In general, the catalysts may be classified as acids and metal halides. As will be explained below, both types of catalysts are acid-acting catalysts in the modern sense of the term. Some metals (e.g., sodium, copper, and iron) are catalysts for the polymerization of alkenes, especially ethylene. They are active probably because they can combine with one of the pi electrons of the alkene and form a free radical which can then initiate a chain reaction (p. 25). 

Braese, S. de Meijere, A. Gross-Coupling of Organic Halides with Alkenes the Heck Reaction. In Metal-Catalyzed Cross-Coupling Reactions, 2nd ed. de Meijere, A., Diederich, F., Eds. Wiley-VCH Weinheim, 2004 pp 217-315. 

Alkynes. Because of their less nucleophilic character, alkynes react less readily with hydrogen halides than do alkenes and often require the use a metal halide catalyst. Vinyl halides are formed in the reaction with one equivalent of HHlg. They may react further in an excess of the reagent to yield geminal dihalides. High yields of these compounds can be achieved. The addition of HC1 to acetylene was studied in detail because of the practical importance of the product vinyl chloride (see Section 6.2.4). 

With less reactive alkenes, particularly those bearing one or more halogens, it is often advisable to add a Lewis acid catalyst to the reaction (equations 32—41 ).61-66 The metal halides AlCb, FeCb, SnCb and BiCb have been most commonly employed as catalysts.29... 

Alkenes and alkynes coordinate to transition metals and undergo a variety of reactions, and are very important substrates for transition metal-catalysed reactions. Their reactions with halides, cyclization via carbene complexes, hydrogenation, and oxidative reactions with Pd(II) are treated in Sections 3.2, 8.2, 10.1 and 11.1, respectively. The many other reactions of alkenes and alkynes as main reactants are treated in this chapter. 

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