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    Grignard 3

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    elbron
    The Grignard reaction is a prominent process for forming carbon-carbon bonds that was discovered in 1900. It involves an organomagnesium species called a Grignard reagent reacting with an electrophilic substrate. While the Grignard reagent is typically thought to act as a nucleophile, evidence suggests an alternative radical or single electron-transfer mechanism may also occur, especially with certain ketone substrates. The exact mechanism of the Grignard reaction has remained elusive due to the variety of chemical species present in Grignard reagent solutions. Elucidating this mechanism could help improve the design of more efficient Grignard reaction variants.

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    Grignard 3

    Uploaded by

    elbron
    36 views2 pages
    The Grignard reaction is a prominent process for forming carbon-carbon bonds that was discovered in 1900. It involves an organomagnesium species called a Grignard reagent reacting with an electrophilic substrate. While the Grignard reagent is typically thought to act as a nucleophile, evidence suggests an alternative radical or single electron-transfer mechanism may also occur, especially with certain ketone substrates. The exact mechanism of the Grignard reaction has remained elusive due to the variety of chemical species present in Grignard reagent solutions. Elucidating this mechanism could help improve the design of more efficient Grignard reaction variants.

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    The Grignard reaction is a prominent process for forming carbon-carbon bonds that was discovered in 1900. It involves an organomagnesium species called a Grignard reagent reacting with an electrophilic substrate. While the Grignard reagent is typically thought to act as a nucleophile, evidence suggests an alternative radical or single electron-transfer mechanism may also occur, especially with certain ketone substrates. The exact mechanism of the Grignard reaction has remained elusive due to the variety of chemical species present in Grignard reagent solutions. Elucidating this mechanism could help improve the design of more efficient Grignard reaction variants.

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    36 views2 pages

    Grignard 3

    Uploaded by

    elbron
    The Grignard reaction is a prominent process for forming carbon-carbon bonds that was discovered in 1900. It involves an organomagnesium species called a Grignard reagent reacting with an electrophilic substrate. While the Grignard reagent is typically thought to act as a nucleophile, evidence suggests an alternative radical or single electron-transfer mechanism may also occur, especially with certain ketone substrates. The exact mechanism of the Grignard reaction has remained elusive due to the variety of chemical species present in Grignard reagent solutions. Elucidating this mechanism could help improve the design of more efficient Grignard reaction variants.

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    The Grignard reaction is a prominent textbook process to form carbon–carbon

    bonds.(1) In this reaction, the so-called Grignard reagent, an organomagnesium


    species RMgX where R is an organic residue and X is a halogen (usually Cl or
    Br), promotes the addition of its organic residue to an electrophilic substrate.
    Discovered by Victor Grignard(2) already in 1900, Grignard reagents rapidly
    became important compounds for organic synthesis in research laboratories and
    in industry.(3) Even though the reaction today is applied to a large variety of
    electrophiles, the prototypic substrates are carbonyl moieties R1R2(C═O) yielding
    a magnesium-alcoholate (eq 1). The R1 and R2 residues usually include hydrogen
    as well as alkyl-, vinyl-, or aryl- groups. The Grignard reaction usually takes place
    in ethereal solvents, the final alcohol product being obtained by hydrolysis.
    Despite more than 100 years of extensive studies, the mechanism of this
    reaction has remained elusive, with little quantitative information and missing
    consensus. Difficulties in elucidating this mechanism are prominently related to
    the fact that the ethereal solutions of Grignard reagents contain a variety of
    chemical species.(4,5) In fact, the nominal reactant RMgX is just a condensed
    representation of numerous mono- and polymetallic molecules that coexist at
    equilibrium (eq 2) and whose relative abundance depends on the nature of R and
    X as well as the experimental condition
    Furthermore, while the polarity of the C(δ−)–Mg(δ+) bond suggests that the Grignard
    reagent acts as a nucleophile, it has been argued that an electron-transfer
    mechanism may occur in the presence of appropriate substrates.(5)
    This multifaceted aspect of the Grignard chemistry is per se fascinating; in fact,
    the lack of understanding of its molecular mechanisms has slowed progress in
    the rational design of more efficient variants of the reaction. Indeed, while the
    efficiency of Grignard reagents has been heuristically improved, for example by
    the synergistic effect of additives like alkali ions, the reasons for these
    improvements remain unclear.(7) Elucidation of the mechanism of the basic
    Grignard reaction is the required step to better understand a wide variety of
    related reactions.
    Although the nucleophilic mechanism (also known as the polar mechanism) is
    currently recognized in the literature as a route to the alcohol product, no
    experimental study was able to assign the relative reactivity of the various forms
    of the organomagnesium species. In parallel, experimental evidence consistently
    supported the presence of an alternative mechanism (called radical or single
    electron-transfer mechanism) involving the formation of radical intermediates
    (Figure 1). In particular, products were detected, which could not originate from a
    nucleophilic addition but could be only obtained through a combination of organic
    radicals.(8−15) Furthermore, electron spin resonance spectroscopy identified the
    presence of ketyl radicals in benzophenone/Grignard reagent mixtures.
    (16) Factors favoring the radical mechanism were searched. Thus, using the
    distribution of products as an indicator for the mechanism, Ashby and co-workers
    inferred that an electron-transfer mechanism depends on the reduction potential
    of the substrate, the oxidation potential of the Grignard reagent, and the polarity
    of the solvent. Ketones with low reduction potential favored the radical
    mechanism. Indeed, a radical-type reaction was established for aromatic and
    conjugated ketones (such as benzophenone and fluorenenone) in the case of
    tertiary as well as primary Grignard reagents.(14)

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