Nozaki–Hiyama–Kishi reaction

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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

chromic chloride by lithium aluminium hydride to which was added benzaldehyde and allyl chloride
:

NHK reaction 1977

Compared to

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.[3]

In 1983 the scope was extended by the same authors to include

co-catalyst.[6]

NHK reaction 1986 Nozaki

In the same year Yoshito Kishi et al. independently discovered the beneficial effects of nickel in his quest for palytoxin:[7]

NHK reaction Kiski 1986

Palladium acetate
was also found to be an effective cocatalyst.

Reaction mechanism

Nickel is the actual

carbonyl group in a nucleophilic addition
.

NHK reaction mechanism

The amount of nickel used should be low as a direct alkene coupling to a diene is a side reaction.[8]

Related reactions are the Grignard reaction (magnesium), the Barbier reaction (zinc) and addition reactions involving organolithium reagents.

References

  1. doi:10.1002/0471264180.or064.03
  2. doi:10.1021/ja00451a061
  3. doi:10.1039/C1SC00116G
    .
  4. doi:10.1016/S0040-4039(00)88417-8
  5. doi:10.1021/ja00279a068
  6. doi:10.1039/C2CS15249E
  7. doi:10.1021/ja00278a057
  8. ^ Kazuhiko Takai, Koichi Sakogawa, Yasutaka Kataoka, Koichiro Oshima, and Kiitiro Utimoto (1998). "Preparation and reactions of alkenylchromium reagents: 2-Hexyl-5-phenyl-1-penten-3-ol". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 9, p. 472.
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