Catalysts in Organic Synthesis

and Addition reactions

What is a Catalyst?

Catalysis is the process in which the rate of a chemical reaction is

either increased or decreased by means of a chemical substance
known as a catalyst

Types of Catalytic reactions

a.
b.

Heterogeneous
Homogeneous

Catalytic Hydrogenation

Hydrogenation is the chemical reaction that results from the addition of

hydrogen. The process is usually employed to reduce or saturate organic
compounds. The process typically constitutes the addition of pairs of hydrogen
atoms to a molecule. Catalysts are required for the reaction to be usable; noncatalytic hydrogenation takes place only at very high temperatures. Hydrogen
adds to double and triple bonds in hydrocarbons.

Application in the food industry:

Vanaspathy preparation
(unsaturated fatty acids(oils) are converted into
saturated derivatives)

Ziegler-Natta Polymerization

Karl Ziegler and Giulio Natta

were awarded the Nobel Prize in
Chemistry in 1963 for their
discovery of these titanium-based
catalysts.
Based on titanium compounds and
organometallic
aluminium
compounds, such as undefined
methylaluminoxane
or
welldefined
triethyl
aluminium,
(C2H5)3Al.
Ziegler-Natta catalyst can be used
to prepare stereoregular polymers
like isotactic, syndiotactic and
atactic.

R
Cl

Cl

Ti

Cl
Cl

Vacant
site

Structure of the active catalyst

species

Diels-Alder Reaction
The Diels-Alder reaction, namely [4+2]- cycloaddition of a diene and a
dienophile as discovered in 1928, is one of the most powerful method for the
regio- and stereo-specific preparation of carbocyclic and heterocyclic ring
systems. Lewis acid increase the rate of the reaction and its regio, endo, and
face selectivity by coordination with the dienophile, i.e. with a conjugated
carbonyl or nitrile group.

R2
R1

Y +

R1

Y R2

Interaction between the centers of the frontier orbital having the largest orbital
coefficients.
For dienophile with electron-withdrawing or electron releasing substituents,
orbital coefficients are higher at -carbon.
For the regiochemical relationships can be best understood by considering the
atomic coefficients of the frontier orbitals.
The regiochemistry can be predicted on the basis of the generalisation that the
strongest dienes with electron withdrawing or electron releasing substituents at
C-1 carbon, the orbital coefficients are higher at C-4. So C-4 of diene and carbon of the dienophile interact more strongly leading to ortho like orientation.

Green Chemistry

What is Green Chemistry?

Green chemistry is the use of chemistry for pollution prevention.

Pollution prevention is the use of materials, processes, or practices

that reduce or eliminate the creation of pollutants or wastes at the
source. It includes practices that reduce the use of hazardous and
nonhazardous materials, energy, water, or other resources as well as
those that protect natural resources through efficient use. -U.S. EPA
The design of chemical products and processes that are more
environmentally benign.
Encompasses all aspects and types of processes that reduce negative
impacts to human health and the environment.
Focuses on processes and products that reduce or eliminate the use
and generation of hazardous substances.
Became a formal focus of the U.S. EPA in 1991 with the formation of
their Green Chemistry Program.
Promotes research, development and implementation of inventive
chemical technologies that accomplish pollution prevention in
both a scientifically-sound and cost-effective manner.

What is Green Chemistry?

Benign
Disposal
Recycle/Re-use
Reduce

Chemical usage
- Energy usage

Hazardous materials, processes

Replace -Inefficient processes
Non-sustainable components

Environmental Chemistry versus

Green Chemistry

Environmental chemistry is the study of sources, reactions, transport

and fate of chemical entities in the air, water, and soil environments as
well as their effects on human health and the environment.
Focuses on the environmental management of chemicals.
Concerned not only with the chemical pollutants in the environment but
also with the behavior of natural chemicals in natural systems.
When chemical use results in environmental contamination, it is
necessary to set standards for acceptable concentrations in water, air, soil
and biota.
Has focused on the effects of what man has put into the environment and
how to deal with and remediate contamination sites.
Dilution is the solution to pollution
In contrast, green chemistry focuses on how to change what human
activity puts into the environment in order to eliminate or reduce effects
and prevent contamination sites.
An milligram of prevention is worth a kilogram of cure.

GREEN CHEMISTRY
Green chemistry is the design of chemical products and processes
that reduce or eliminate the use and generation of hazardous
substances- Sustainable Science
It encompasses all aspects and types of chemical processes
including synthesis, catalysis, analysis, monitoring, separations, and
reaction conditions that reduce negative impacts on human health and
the environment relative to the current state of the art.

The twelve principles of green chemistry/ engineering proposed by

Anastas and Warner, 1998, Anastas and Zimmerman, 2003,serve as
guidelines for practicing chemists/ engineers in developing and
assessing how green a synthesis, compound, process, design or
technology is .