Organic Chemistry And Reaction Mechanisms Codexery

Grignard reaction

Organometallic reaction forming carbon–carbon bonds via Grignard reagents.

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The Grignard reaction is an organometallic chemical reaction where carbon alkyl, allyl, vinyl, or aryl magnesium halides add to carbonyl groups of aldehydes or ketones under anhydrous conditions.[1] Carbon–carbon bond formation is a key application of this reaction.[1]

Quick Facts

Discovered by
François Auguste Victor Grignard
Field
Organometallic chemistry
Nationality
French
Known for
Grignard reaction and Grignard reagents
Nobel prize
1912 Nobel Prize in Chemistry

Facts from the source article.

Key facts and history

French chemist François Auguste Victor Grignard discovered the reaction and reagents at the University of Nancy, describing them in 1900.[2] The reaction of an organic halide with magnesium provides a Grignard reagent, not a Grignard reaction.[3] The Merck Index, published online by the Royal Society of Chemistry, acknowledges the classical definition followed by a more modern interpretation extending the scope.[4] The addition typically proceeds through a six-membered ring transition state.[5]

The Grignard reaction is conducted under anhydrous conditions to prevent the reagent from acting as a base instead of a nucleophile.[6] For discovering this reaction, François Auguste Victor Grignard received the 1912 Nobel Prize in Chemistry.[2] A broader interpretation among some chemists includes all reactions where Grignard reagents combine with any electrophilic species.[7] The carbon atom bonded to magnesium becomes nucleophilic and targets the electrophilic carbon within a carbonyl group.[5]

To exclude moisture, the reaction flask for a Grignard reaction is kept under an inert atmosphere.[8]

What the research sources say

The behavior of Grignard reagents can be modified in the presence of other metals, as noted in a 2000 review by Woodward in Chemical Society Reviews.[9][10] Maruyama and Katagiri authored a 1989 paper in the Journal of Physical Organic Chemistry that examines the Grignard reaction's mechanism.[11] According to a 2020 computational study, whether the mechanism follows a polar or radical pathway depends on the substrate, with the carbonyl compound's reduction potential being a critical factor.[12] Turbo-Grignard reagents exhibit greater chemoselectivity than standard Grignard reagents; for instance, esters, amides, and nitriles remain unreactive toward them.[13]

References

  1. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: ; Chapter 19: Carboxylic Acids. Organic Chemistry 4e Carey. mhhe.com; Ouellette, "Organic Chemistry", Elsevier, 2014-01-01, p. 491–534; Shirley, "The Synthesis of Ketones from Acid Halides and Organometallic Compounds of Magnesium, Zinc, and Cadmium", Org. React., 1954, p. 28–58; Huryn, "Comprehensive Organic Synthesis, Volume 1: Additions to C—X π-Bonds, Part 1", Elsevier Science, 1991, p. 49–75 (we also read that source) en.wikipedia.org
  2. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: texte, "Comptes rendus hebdomadaires des séances de l'Académie des sciences / publiés... par MM. les secrétaires perpétuels", Gallica, 1900-01-01; Grignard, V., "Sur quelques nouvelles combinaisons organométaliques du magnésium et leur application à des synthèses d'alcools et d'hydrocabures", Compt. Rend., 1900, p. 1322–25 (original not read by us) en.wikipedia.org
  3. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (19 (original not read by us) en.wikipedia.org
  4. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: "Grignard Reaction The Merck Index Online", www.rsc.org (original not read by us) en.wikipedia.org
  5. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Maruyama, "Mechanism of the Grignard reaction", J. Phys. Org. Chem., 1989, p. 205–213 (we also read that source) en.wikipedia.org
  6. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Ouellette, "Organic Chemistry", Elsevier, 2014-01-01, p. 491–534 (we also read that source) en.wikipedia.org
  7. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: ; "Grignard Reaction The Merck Index Online", www.rsc.org (original not read by us) en.wikipedia.org
  8. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Carey, "Grignard reagent", Britannica (original not read by us) en.wikipedia.org
  9. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Woodward, "Decoding the 'black box' reactivity that is organocuprate conjugate addition chemistry", Chemical Society Reviews, 2000-01-01, p. 393–401 (we also read that source) en.wikipedia.org
  10. Simon Woodward, "Decoding the ‘black box’ reactivity that is organocuprate conjugate addition chemistry", Chemical Society Reviews (2000), doi:10.1039/b002690p. OpenAlex metadata CC0; paper not read. doi.org
  11. Kazuhiro Maruyama, "Mechanism of the Grignard reaction", Journal of Physical Organic Chemistry (1989), doi:10.1002/poc.610020303. OpenAlex metadata CC0; paper not read. doi.org
  12. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Ashby, "Direct evidence supporting a single electron transfer pathway in the reduction of ketones by primary, secondary, and tertiary Grignard reagents", Journal of the American Chemical Society, August 1981, p. 4983–498; Peltzer, "The Grignard Reaction – Unraveling a Chemical Puzzle", Journal of the American Chemical Society, 2020-02-12, p. 2984–2994 (original not read by us) en.wikipedia.org
  13. Wikipedia, "Grignard reaction" (CC BY-SA 4.0), which cites: Hermann, "Comprehensive Study of the Enhanced Reactivity of Turbo-Grignard Reagents*", Angewandte Chemie International Edition, 2023 (we also read that source) en.wikipedia.org

Each numbered sentence above was checked against the source it cites before publication. Sentences citing Wikipedia adapt text from the English Wikipedia article Grignard reaction (contributors), used under CC BY-SA 4.0; this entry is available under the same licence. Other sources were used for facts only; no text or images are copied from them.

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Sources

Compiled from Wikipedia and the sources listed below. Text from Wikipedia is available under CC BY-SA 4.0; this entry is adapted from it.

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