Hydrocarbo Acidity and Metalation<sup>1</sup>

Morton, Avery A.; Claff, Chester E.

doi:10.1021/jo01113a005

Cited by 9 publications

(3 citation statements)

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“…Recently Morton (48) has shown that amylsodium will metálate m-fert-butylphenylsodium in the presence of sodium ¿erí-pentoxide to produce the 3,5-disodio product in 16 per cent yield as judged by carbonation to 5-ferf-butylisophthalic acid. Under similar conditions p-¿er¿-butylphenylsodium does not react.…”

Section: VIImentioning

confidence: 99%

Metalations With Organosodium Compounds

Benkeser¹,

Foster²,

Sauve³

et al. 1957

Chem. Rev.

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Section: VIImentioning

confidence: 99%

Metalations With Organosodium Compounds

Benkeser¹,

Foster²,

Sauve³

et al. 1957

Chem. Rev.

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“…Despite the synthetic promise of such species, the potential of multimetalation remains underutilized, even in organolithium chemistry 3,16,17,27,28 . Double sodiation via deprotonation has been reported 3,14,16,17,[29][30][31][32][33][34][35][36][37][38][39][40][41] , but efficient triple or quadruple sodiation has not been known to date. Our halogen-sodium exchange method enabled the regioselective access to tri-and tetrasodiated compounds (Fig.…”

Section: Resultsmentioning

confidence: 99%

Halogen–sodium exchange enables efficient access to organosodium compounds

et al. 2021

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With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used—and are overshadowed by organolithium compounds—because of a lack of convenient and efficient preparation methods. Here we report a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking β-hydrogens, which retards undesired reactions, such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen–sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents.

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“…The initial step in a metalation reaction is the coordination between the metal and the atom bearing the most acidic hydrogen.5• This initial coordination step has been viewed as an acid-base exchange by some authors,5• 162, íes,221,230,231 an(j as an electrophilic attack on the cation of the organoalkali compound on a carbon atom with increased electron density. 232 The former is presently the more accepted theory.…”

Section: Mechanism and Kineticsmentioning

confidence: 99%