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Nozaki–Hiyama–Kishi reaction

The Nozaki–Hiyama–Kishi reaction is a nickel/chromium coupling reaction forming an alcohol from the reaction of an aldehyde with an allyl or vinyl halide. In their original 1977 publication, Tamejiro Hiyama and Hitoshi Nozaki reported on a chromium(II) salt solution prepared by reduction of chromic chloride by lithium aluminium hydride to which was added benzaldehyde and allyl chloride:

Reaction mechanism
Nickel is the actual catalyst when small amounts of a nickel salt are added to the reaction. Nickel(II) chloride is first reduced to nickel(0) with 2 equivalents of chromium(II) chloride (as sacrificial catalyst) leaving chromium(III) chloride. The next step is oxidative addition of nickel into the carbon to halide bond forming an alkenylnickel R–Ni(II)–X intermediate followed by a transmetallation step exchanging NiX with a Cr(III) group to an alkenylchromium R–Cr(III)–X intermediate and regenerating Ni(II). This species reacts with the carbonyl group in a nucleophilic addition. : The amount of nickel used should be low as a direct alkene coupling to a diene is a side reaction. Related reactions are the Grignard reaction (magnesium), the Barbier reaction (zinc) and addition reactions involving organolithium reagents. ==References==
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