P Pr re ef fa ac ce e
Thes are the times of highly sophisticated computer programs that lead to pretty
t
pictures about how an organic reaction works. Nevertheless, the knowledge of the
mechanism of an organic reaction is still derived from very hard experimental
work and the ability to process and to get information from the data obtained. The
interpretation of the experimental data is a key point in the formation of organic
chemists, independent of their future work. It is sometimes confusing to learn how
to do this in a jumble of equations, theoretical studies, and physical-chemistry postulates. The approach we have chosen for this work is a practical one. Instead of
formulating study mechanisms from the diverse theories and experimental methods in the classical way, the aim of this book is to discuss a series of selected examples of organic reaction mechanisms to understand how they have been proposed.
All the cases presented have been taken from recent literature and deal with the
formulation and experimental determination of a mechanistic proposal. They are
based on real cases that demonstrate how nowadays organic chemists are still
deeply concerned about insights into a reaction. Through the book we use any type
of information that the authors of the original work considered necessary in the
elucidation of the reaction mechanism. This includes spectroscopic data, kinetic
and thermodynamic data, isotopic labelling, theoretical studies … and of course,
the knowledge of the reactivity of organic compounds.
The examples have been ordered into three levels. Level 1 is dedicated to revising fundamental concepts regarding the elucidation of an organic reaction mechanism. The subjects discussed in this level will be the tools to be used later in levels
2 and 3. Level 1 starts with the most immediate source of information when studying an organic reaction mechanism, the structure and stereochemistry of the react t
tion products. Basic concepts regarding crossover experiments, neighboring group
participation and classical/nonclassical carbocations are followed by some examples that illustrate the use of isotopic labelling in mechanistic studies. The importance of data obtained from kinetic measurements is discussed later and subjects
like catalysis in solution, Hammett constants, activation parameters and kinetic
isotope effects are revised. To complete this first part of the book, there are some
examples dedicated to revising the different types of pericyclic reactions such as
cycloadditions, electrocyclic ring closures and sigmatropic rearrangements.
Once the fundametal concepts have been established, they are all combined in
the discussion of the collection of examples proposed in levels 2 and 3. Now the
cases have been placed in order of increasing difficulty from easy to medium in
level 2 and medium to difficult in level 3, mixing the different techniques and data
to understand the different aspects of the example under discussion. All examples
are treated in detail following the same methodology: introduction, experimental
data and discussion. Key points, additional references and solved questions related
to the main subject studied are also included.
Thes are the times of highly sophisticated computer programs that lead to pretty
t
pictures about how an organic reaction works. Nevertheless, the knowledge of the
mechanism of an organic reaction is still derived from very hard experimental
work and the ability to process and to get information from the data obtained. The
interpretation of the experimental data is a key point in the formation of organic
chemists, independent of their future work. It is sometimes confusing to learn how
to do this in a jumble of equations, theoretical studies, and physical-chemistry postulates. The approach we have chosen for this work is a practical one. Instead of
formulating study mechanisms from the diverse theories and experimental methods in the classical way, the aim of this book is to discuss a series of selected examples of organic reaction mechanisms to understand how they have been proposed.
All the cases presented have been taken from recent literature and deal with the
formulation and experimental determination of a mechanistic proposal. They are
based on real cases that demonstrate how nowadays organic chemists are still
deeply concerned about insights into a reaction. Through the book we use any type
of information that the authors of the original work considered necessary in the
elucidation of the reaction mechanism. This includes spectroscopic data, kinetic
and thermodynamic data, isotopic labelling, theoretical studies … and of course,
the knowledge of the reactivity of organic compounds.
The examples have been ordered into three levels. Level 1 is dedicated to revising fundamental concepts regarding the elucidation of an organic reaction mechanism. The subjects discussed in this level will be the tools to be used later in levels
2 and 3. Level 1 starts with the most immediate source of information when studying an organic reaction mechanism, the structure and stereochemistry of the react t
tion products. Basic concepts regarding crossover experiments, neighboring group
participation and classical/nonclassical carbocations are followed by some examples that illustrate the use of isotopic labelling in mechanistic studies. The importance of data obtained from kinetic measurements is discussed later and subjects
like catalysis in solution, Hammett constants, activation parameters and kinetic
isotope effects are revised. To complete this first part of the book, there are some
examples dedicated to revising the different types of pericyclic reactions such as
cycloadditions, electrocyclic ring closures and sigmatropic rearrangements.
Once the fundametal concepts have been established, they are all combined in
the discussion of the collection of examples proposed in levels 2 and 3. Now the
cases have been placed in order of increasing difficulty from easy to medium in
level 2 and medium to difficult in level 3, mixing the different techniques and data
to understand the different aspects of the example under discussion. All examples
are treated in detail following the same methodology: introduction, experimental
data and discussion. Key points, additional references and solved questions related
to the main subject studied are also included.