Nozaki–Hiyama–Kishi reaction
| Nozaki-Hiyama-Kishi reaction | |
|---|---|
| Named after |
Hitoshi Nozaki Tamejiro Hiyama Yoshito Kishi |
| Reaction type | Coupling reaction |
| Identifiers | |
| Organic Chemistry Portal | nozaki-hiyama-coupling |
| RSC ontology ID | RXNO:0000191 |
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:
Compared to Grignard reactions, this reaction is very selective towards aldehydes with large tolerance towards a range of functional groups such as ketones, esters, amides and nitriles. Enals give exclusively 1,2-addition. Solvents of choice are DMF and DMSO, one solvent requirement is solubility of the chromium salts. Nozaki-Hiyama-Kishi reaction is a useful method for preparing medium-size rings.
In 1983 the scope was extended by the same authors to include vinyl halides or triflates and aryl halides. It was observed that the success of the reaction depended on the source of chromium(II) chloride and in 1986 it was found that this is due to nickel impurities. Since then nickel(II) chloride is used as a co-catalyst.
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