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Wacker Process
Catalytic cycle of the process
Twp possible mechanisms
1) the reaction is carried out in an aqueous medium in the presence of HCl;
2) terminal alkenes react much faster than internal or 1,1-disubstituted
alkenes and they are almost exclusively converted to the corresponding methyl
ketones;
3) terminal alkenes can be viewed as masked ketones for synthetic purposes;
4) under the reaction conditions, internal alkenes are not oxidized to any
appreciable extent;
5) α,β-unsaturated ketones and esters are oxidized regioselectively to the
corresponding β-keto compounds using catalytic amounts of Na2PdCl4 and
TBHP or H2O2 as co-oxidants;
6) when the oxidation is carried out in the presence of nucleophiles other than
water, the process is called the Wacker-type oxidation, which can take place
both inter- and intramolecularly.
The general features of this reaction
Heck Reaction
Product depends on the nature of the R group
Presence of base like Et3N is important in this reaction , why?
Movement of double bond
Negishi Reaction
Application of Negishi Reaction
Sonogashira coupling
Cu is used as co-catalyst
The geometry of the alkene is generally preserved
Buchwald-Hartwig Coupling
Stille Reaction (Migita-Kosugi-Stille coupling)
Stille works with SP carbons as well.
Stille reaction with the carbonylation
+ ?
+
CO
Intramolecular attack
Dendrimer-Encapsulated Pd Nanoparticles
Dendrimers are organic
molecules with functional
groups at their periphery
These dendrimers are used as templates for the synthesis of monodisperse Pd
nanoparticles.
G4-OH was mixed with 0.1 ml of 10 mM aq. K2PdCl4 in 10 ml water. NaBH4 was used to
reduce the Pd nanoparticles.
The size of the nanoparticles are about 2 nm.
Advantages of Den-Pd
Solubility is controlled by chemical composition at the periphery.
The nanoparticles are encapsulated within the dendrimer, so no ligands are needed for
stabilization.
They are small which gives high surface area to volume ratio.
Stille reaction
G4-OH, Pd
SnCl3
+
Control experiments:
Following control experiments to confirm that Pd nano is the active catalyst.
1. Same reaction performed without Pd (only with dendrimers)
2. reaction with Dendrimers and Pd2+
precursors.
3. Reaction with Dendrimer with Au nanoparticles
No Stille reaction occurred
Ι
COOH
COOH
Only Pd
More control experiments to understand the mechanism
Model for the catalytic activity
Catalytic poisoning occurs for the ortho isomer due to the interaction of carboxylic groups
with the Pd atoms.
Kumada coupling
Simple steps and cheap raw materials
Industrial scale production of styrene
Buchwald-Hartwig Coupling
One of the advantageous of using chloro compound is lower cost
Hydroamination
Definition: Hydroamination is the formal addition of an N-H bond to C-C multiple
bonds.
 Direct addition of amines can lead to 2 regioisomeric amines:
- The Markovnikov product
- The anti-Markovnikov product
R
NR'2
R
H
H
R
NR'2
H NR'2+
anti-Markovnikov Markovnikov
Base catalyzed hydroaminatin of olefines
Hydroamination of alkynes via metal imide

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