Halogenation of Organometallics

Larock, Richard C.; Zhang, Li

doi:10.1002/9781118662083.cot04-013

Cited by 4 publications

(5 citation statements)

References 155 publications

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“…Carboxylic anhydrides are highly valuable reagents in organic synthesis, commonly used in acylation reactions of amines for the synthesis of amides. [1] Amidation reactions like these are of utmost importance in organic synthesis from laboratory to industrial scale, [2] since amides are among the most common functional groups in medicinal chemistry. [3] The valorization of carboxylic acids is important because they are naturally abundant, inexpensive, safe, and readily available starting materials.…”

Section: Introductionmentioning

confidence: 99%

“…Considering the enormous importance of dehydration reactions in organic synthesis, [1] electrochemical dehydrations could offer many new interesting reactivities to explore, which will help to eliminate commonly accepted limits and myths about synthetic electrochemistry. [16] In this report, we further developed the electrochemical dehydration of dicarboxylic acids for the synthesis of cyclic carboxylic anhydrides.…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides

Schneider,

Häring,

Waldvogel

2024

Chemistry A European J

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An intramolecular electrochemical dehydration reaction of dicarboxylic acids to their cyclic anhydrides is presented. This electrolysis allows dicarboxylic acids as naturally abundant, inexpensive, safe, and readily available starting materials to be transformed into carboxylic anhydrides under mild reaction conditions. No conventional dehydration reagent is required. The obtained cyclic anhydrides are highly valuable reagents in organic synthesis, and in this report, we use them in‐situ for acylation reactions of amines to synthesize amides. This work is part of the recent progress in electrochemical dehydration, which – in contrast to electrochemical dehydrogenative reactions for example – is an underexplored field of research. The reaction mechanism was investigated by 18O isotope labelling, revealing the formation of sulfate by electrochemical oxidation and hydrolysis of the thiocyanate supporting electrolyte. This transformation is not a classical Kolbe‐electrolysis, because it is non‐decarboxylative, and all carbon atoms of the carboxylic acid starting material are contained in the carboxylic anhydride. In total, 20 examples are shown with NMR yields up to 71%.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electrochemical Dehydration of Dicarboxylic Acids to Their Cyclic Anhydrides

Schneider,

Häring,

Waldvogel

2024

Chemistry A European J

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“…The ability to simultaneously introduce two vicinal functional groups to the double bond makes it a powerful synthetic tool. In practice, however, the regioselectivity of electrophilic additions is not always easy to control . Typically, site-selectivity is determined by the Markovnikov rule, − but it can be overrun by conjugative effects − or intramolecular nucleophilic participation. , The introduction of the silyl substituent provides a way to control regioselectivity.…”

Section: Introductionmentioning

confidence: 99%

β-Boron Effect Enables Regioselective and Stereospecific Electrophilic Addition to Alkenes

Fan

Luo

et al. 2023

J. Am. Chem. Soc.

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Electrophilic addition to alkenes is a textbook-taught reaction, yet it is not always possible to control the regioselectivity of addition to unsymmetrical 1,2-disubstituted substrates. We report the observation and applications of the β-boron effect that accounts for high regioselectivity in electrophilic addition reactions to allylic MIDA (N-methyliminodiacetic acid) boronates. While the wellestablished β-silicon effect bears partial resemblance to the observed reactivity, the silyl group is typically lost during functionalization. In contrast, the boryl moiety is retained in the product when B(MIDA) is used as the nucleophilic stabilizer. Mechanistic studies elucidate the origin of this effect and demonstrate how σ(C−B) hyperconjugation helps stabilize the incipient carbocation. This transformation represents a rare example of the stereospecific hydrohalogenation of secondary allyl MIDA-boronates that proceeds in a syn-fashion.

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“…Primary amines and nitriles are key building blocks for the preparation of various important pharmaceutical products, agrochemicals, dyes, pigments, plastics, surfactants, and various fine chemicals. 1–4 Among the several synthetic methodologies known for their synthesis, 5–11 the transformation from primary amide is considered as a convenient, straightforward and useful synthetic route. 12,13 Traditionally, the amide to amine transformation is performed by using a stoichiometric or excess amount of reactive alumino- or borohydrides, which suffer from tolerance of various common functional groups and separation of a stoichiometric amount of by-products.…”

Section: Introductionmentioning

confidence: 99%