Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation: Proposed mechanistic pathways

(1) Oxidative addition of ArX on copper(I) resulting in anintermediate Cu(III) species.

(2) Aryl radical intermediates, either via single electron transfer(SET) or via halide atom transfer (AT).

(3) 𝜎𝜎-bond metathesis through a four-centre intermediate.

(4) 𝜋𝜋-complexation of copper(I) on ArX.

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation: Proposed mechanistic pathways

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving 𝝅𝝅-complexation

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving oxidative addition/reduction elimination

N

O

I

CuClN

O

Cl

CuCNN

O

CN

DMF, reflux

DMF, reflux

PhCOOH

N

O

H

O

Cu

OH+

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving oxidative addition/reduction elimination

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving single electron transfer (SET) and the SRN1

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving single electron transfer (SET) and the SRN1

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:Mechanistic pathways involving 𝝈𝝈-bond metathesis

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides: catalyst solubility and catalyst deactivation

Cu/3 ) 1:2 Cu/3 ) 1:7

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Dependence of the reaction rate on amide concentration ([2])

Cu/3 ) 1:2 Cu/3 ) 1:10

0.93 M (green times signs), 0.8 M (black times signs), 0.7 M (red squares),0.6 M (blue times signs)

Both the increasing slope of the rateCurves.

Thereis a zero-order rate dependence on [1,2-diamine] and a positiveorderdependence on [amide].

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Dependence of the reaction rate on amide concentration ([2])

Cu/3 ) 1:2 Cu/3 ) 1:10

0.93 M (green times signs), 0.8 M (black times signs), 0.7 M (red squares),0.6 M (blue times signs)

Both the increasing slope of the rateCurves.

Thereis a zero-order rate dependence on [1,2-diamine] and a positiveorderdependence on [amide].

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Dependence of the reaction rate on aryl iodide concentration

Cu/3 ) 1:2 Cu/3 ) 1:10

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:(1). Dependence of the reaction rate on K3PO4 concentration

(2). Hammett plot derived from the observed rate constants of theN-arylation of 2-pyrrolidinone (2) with a series of para-substituted aryliodides.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Synthesis and Characterization of Cu(I) Amidates.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Kinetics Studies: N-Arylation of Cu(I) Amidate with ArylIodides.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Kinetics Studies: N-Arylation of Cu(I) Amidate with ArylIodides.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (A) Overview.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (A) Overview.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (A) Overview.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (B) Controlling the Resting State ofthe Catalyst with the 1,2-Diamine Ligand.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (B) Controlling the Resting State ofthe Catalyst with the 1,2-Diamine Ligand.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (B) Controlling the Resting State ofthe Catalyst with the 1,2-Diamine Ligand.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Catalytic Mechanism: (B) Controlling the Resting State ofthe Catalyst with the 1,2-Diamine Ligand.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:Correlation between the Stoichiometric N-Arylation of Cu(I)Amidates and the Cu(I)-Catalyzed N-Arylation of Amides.

Organic Reaction Mechanism Report: The Ullmann Reaction

3. Mechanistic Studies on the Copper-Catalyzed N-Arylation of Amides:

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

2. Mechanistic investigations on the Ullmann condensation:

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

Organic Reaction Mechanism Report: The Ullmann Reaction

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