Organic Reaction

12th Oct 2018/9th Nov/Sec E

ACC 11101/ACC 11102 CHEMISTRY
(3-0-0)

Introduction to Quantum chemistry.Thermodynamic functions, laws of thermodynamics,

properties of entropy, criteria for spontaneity and equilibrium, properties of free energy,
Chemical potential.Phase and reaction equilibria. Electrochemical Systems:
Electrochemical cells and EMF, Applications of EMF measurements, Fuel cells. Kinetics of
Chemical Reactions: Reversible, consecutive and parallel reactions, Steady state
approximation, Chain reactions. Coordination Chemistry: Valence-bond theory, Crystal
Field theory and brief introduction to MO. Introduction to spectroscopy, IR, UV, NMR.
Solid state chemistry and defects. Environmental Chemistry, NOx, CO, CO2.
Stereochemistry: Concept of chirality, center and axis of chirality, examples of
compounds with one and two chiral centers, enatiomers and diastereomers, absolute
and relative configuration, configuration descriptors R/S and E/Z notations, optical
rotation & purity, Named reactions & Green Chemistry.

Recommended Books:
1. S. H. Pine, Organic Chemistry, McGraw Hill, 5th Ed, 1987.
2. R. T. Morrison and R. N. Boyd, Organic Chemistry, Prentice Hall.
3. W. Caruther, Reagents in Organic Chemistry, Cambridge University Press.
 Transition-metal -
catalyzed
reactions

Carbon- Carbon-
Carbon Bond Heteroatom
formation Bond formation

Suzuki-Miyaura Coupling Buchwald-Hartwig amination

Negishi Coupling Ullaman-type reaction
Heck Coupling Chan-Lam-Evans coupling
Stille Coupling
Sonagashira Coupling
Kumada Coupling
Hiyama Coupling
Cross-coupling Reaction

Suzuki Reaction

Stille Reaction

Negishi Reaction

Kumada Reaction

Hiyama Reaction
 Suzuki Reaction
The Reaction

The Suzuki reaction is an organic reaction, classified as a coupling reaction, where the coupling partners are
a boronic acid and an organohalide catalyzed by a palladium(0) complex. It was first published in 1979
by Akira Suzuki and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi
Negishi for their effort for discovery and development of palladium-catalyzed cross couplings in organic
synthesis

Mechanism
Common Pd-catalyst
Application
 Negishi Reaction

The Negishi Coupling, published in 1977, was the first reaction that allowed the preparation of
unsymmetrical biaryls in good yields. The versatile nickel- or palladium-catalyzed coupling of
organozinc compounds with various halides (aryl, vinyl, benzyl, or allyl) has broad scope, and is
not restricted to the formation of biaryls.
 Application

In 2003 Novartis employed a Negishi coupling in the manufacture of PDE472,

a phosphodiesterase type 4D inhibitor, which was being investigated as a drug lead
for the treatment of asthma. The Negishi coupling was used as an alternative to the
Suzuki reaction providing improved yields, 73% on a 4.5 kg scale, of the desired
benzodioxazole synthetic intermediate.
 Heck Reaction

Mechanism
 Sonogashira Coupling

Mechanism
 Buchwald-Hartwig Cross Coupling Reaction
C-N Bond Formation

Mechanism
Common Ligand
 Ullmann Reaction

Mechanism
Ligands/Salts/bases

The most common bases for C-N

couplings are: t- BuONa, t-BuOK,
LHMDS, Cs2CO3, K2CO3, K3PO4,
NaOMe, NaOH, KOH and t-AmONa.

Application
Concept of Atom Economy

 The greater the value of the atom economy, the

better is the reaction to convert all the reactant
atoms to the desired product.
Calculate the atom economy of each of the following conversions

C4H9OH + KBr + H2SO4  C4H9Br + KHSO4 + H2O

136.9 136.2 18.0

136.9
AE   100% = 47.0%
136.9  136.2  18.0

3C4H9OH + PBr3  3C4H9Br + H3PO3

3136.9 82.0

3  136.9
AE   100% = 83.4% Greener
3  136.9  82.0