Styrenes, cobalt-catalyzed Heck reactions

Fig. 54 Cobalt-catalyzed Heck reactions of alkyl halides and styrenes...

Cobalt-catalyzed Heck-type Reaction of Alkyl Halides with Styrenes... 

Ikeda, Y., Nakamura, T., Yorimitsu, H. and Oshima, K. (2002) Cobalt-catalyzed Heck-type reaction of aUcyl halides with styrenes. J. Am. Chem. Soc., 124, 6514-5. 

Other metals can catalyze Heck-type reactions, although none thus far match the versatility of palladium. Copper salts have been shown to mediate the arylation of olefins, however this reaction most probably differs from the Heck mechanistically. Likewise, complexes of platinum(II), cobalt(I), rhodium(I) and iridium(I) have all been employed in analogous arylation chemistry, although often with disappointing results. Perhaps the most useful alternative is the application of nickel catalysis. Unfortunately, due to the persistence of the nickel(II) hydride complex in the catalytic cycle, the employment of a stoichiometric reductant, such as zinc dust is necessary, however the nickel-catalyzed Heck reaction does offer one distinct advantage. Unlike its palladium counterpart, it is possible to use aliphatic halides. For example, cyclohexyl bromide (108) was coupled to styrene to yield product 110. 

A method complementary to the palladium-catalyzed reaction has been reported. A cobalt-phosphine complex catalyzes a Heck-type reaction of alkyl halides with styrenes in the presence of Me3SiCH2MgCl [174]. Trimethylsilylmethylmag-nesium chloride was added to a mixture of styrene and bromocyclohexane in ether in the presence of a catalytic amount of CoCl2(dpph) at O C. Heating the reaction mixture under reflux (35°C) provided 163a in 91% yield (Scheme 3.158). 

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