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α-Alkylation of Ketones via Enolate Ions01:10

α-Alkylation of Ketones via Enolate Ions

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Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Acid Halides to Ketones: Gilman Reagent01:14

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Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
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Acid-Catalyzed α-Halogenation of Aldehydes and Ketones01:21

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By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...
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Nitriles to Ketones: Grignard Reaction00:57

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Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
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Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation01:01

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Benzaldehyde, like formaldehyde, lacks an α hydrogen and cannot enolize to form an enolate. Hence, the reaction of benzaldehyde with a ketone in the presence of an aqueous base forms a single crossed product. This reaction is referred to as Claisen–Schmidt condensation.
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Diverse and Selective Metal-Ligand Cooperative Routes for Activating Non-Functionalized Ketones.

Carlos Ferrer-Bru1, Joaquina Ferrer1, Vincenzo Passarelli1

  • 1Departamento de Catálisis y Procesos Catalíticos, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC - Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.

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Summary
This summary is machine-generated.

Rhodium and iridium complexes activate ketone C-H bonds and add to C=O bonds through unique cooperative metal-ligand reactivity. These atom-efficient reactions proceed without additives, showcasing diverse pathways driven by distinct intermediates.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Reaction Mechanisms

Background:

  • Rhodium and iridium complexes with pyridinyl-amidine ligands (Cp*M(L)) are known catalysts.
  • Ketone functionalization is crucial in organic synthesis.
  • Understanding cooperative metal-ligand reactivity is key to developing new catalytic processes.

Purpose of the Study:

  • To investigate the reactivity of rhodium and iridium complexes with nonfunctionalized ketones.
  • To elucidate the mechanisms of cooperative metal-ligand bond activation and addition reactions.
  • To demonstrate atom-efficient ketone functionalization strategies.

Main Methods:

  • Synthesis and characterization of rhodium and iridium complexes [Cp*M(κ³N,N',N″-L)][SbF₆].
  • Reaction studies with various methyl ketones and fluorinated ketones.
  • Density Functional Theory (DFT) calculations to explore reaction pathways and intermediates.

Main Results:

  • Complexes 1 (Rh) and 2 (Ir) exhibit distinct reactivity modes with ketones.
  • Methyl ketone C(sp³)-H bond activation yields ketonyl compounds.
  • Addition to the ketone C=O bond occurs via different pathways for Rh and Ir, leading to metal-alkoxide derivatives.
  • The rhodium complex can undergo multiple ketone additions.

Conclusions:

  • Cooperative metal-ligand interactions enable diverse and selective ketone functionalization.
  • The observed reactivity is driven by three distinct intermediates, as supported by DFT calculations.
  • These reactions represent 100% atom-efficient methods for C-H bond activation and ketone addition.