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Related Concept Videos

Elimination Reactions02:25

Elimination Reactions

A nucleophile can react with an alkyl halide to give the substitution product by displacing the halogen. Or it can function as a base to give the elimination product by deprotonation of the neighboring carbon to form an alkene. In an elimination reaction, the substrate loses two groups from adjacent carbons forming at least one π bond. The carbon attached to the halogen is called the α carbon, while the adjacent carbon is called the β carbon; hence, these reactions are called β elimination or...
Preparation of Alkynes: Dehydrohalogenation02:34

Preparation of Alkynes: Dehydrohalogenation

Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Acid Halides to Alcohols: LiAlH4 Reduction01:19

Acid Halides to Alcohols: LiAlH4 Reduction

Acid halides are reduced to alcohols in the presence of a strong reducing agent like lithium aluminum hydride.
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
Amides to Amines: LiAlH4 Reduction01:20

Amides to Amines: LiAlH4 Reduction

Amide reduction with strong reducing agents like lithium aluminum hydride proceeds through a nucleophilic acyl substitution to form amines. Primary, secondary, and tertiary amides yield primary, secondary, and tertiary amines, respectively.
Amide reduction requires two equivalents of the reducing agent, acting as a source of hydride ions. As shown in the figure, the reaction is initiated with a nucleophilic attack by the hydride ion at the carbonyl carbon to form a tetrahedral intermediate.
Nitriles to Amines: LiAlH4 Reduction00:55

Nitriles to Amines: LiAlH4 Reduction

Nitriles are reduced to amines in the presence of strong reducing agents like lithium aluminum hydride through a typical nucleophilic acyl substitution. The reaction requires two equivalents of the reducing agent. The reducing agent acts as a source of hydride ions.
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...

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Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
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Beta-aryl eliminations from Rh(I) iminyl complexes.

Pinjing Zhao1, John F Hartwig

  • 1Department of Chemistry, Yale University, PO Box 208107 New Haven, Connecticut 06520-8107, USA.

Journal of the American Chemical Society
|August 18, 2005
PubMed
Summary

This study details beta-Aryl elimination reactions in rhodium iminyl complexes, forming rhodium aryl complexes and nitriles. The research elucidates the mechanism and migratory aptitudes of aryl groups in these transformations.

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Area of Science:

  • Organometallic Chemistry
  • Rhodium Catalysis
  • Reaction Mechanisms

Background:

  • Iminyl complexes are versatile intermediates in organometallic chemistry.
  • Understanding beta-Aryl elimination is crucial for designing catalytic cycles.

Purpose of the Study:

  • To report the synthesis and characterization of rhodium iminyl complexes.
  • To investigate the beta-Aryl elimination reaction pathway and kinetics.
  • To determine the migratory aptitudes of various aryl groups.

Main Methods:

  • Synthesis of iminyl complexes via reaction of [Rh(COE)Cl]2, phosphine, and imines.
  • X-ray diffraction for structural characterization of one complex.
  • Thermal decomposition studies in different solvents (cyclohexane, benzene).
  • Kinetic studies to determine reaction orders with respect to phosphine and nitrile.

Main Results:

  • Rhodium iminyl complexes [Rh(PEt3)3(N=CArAr')] were successfully synthesized.
  • Beta-Aryl elimination proceeded in high yields to form rhodium aryl complexes and free nitriles.
  • Aryl migratory aptitudes were found to be: o-anisyl > phenyl > p-anisyl and o-tolyl.
  • Kinetic studies indicated inverse first-order dependence on phosphine and zero-order on nitrile.

Conclusions:

  • Beta-Aryl elimination likely proceeds via phosphine dissociation to form a 14-electron intermediate.
  • The migratory aptitude of aryl groups is influenced by electronic and steric factors.
  • This work provides insights into the mechanism of C-C bond cleavage in rhodium complexes.