Organic Reaction Mechanisms (Lecture 1)

Why it matters? Mastering reaction mechanisms is a critical

step you must take to begin to understand, as opposed to simply
memorize, chemical reactions in organic chemistry.
 Mechanisms provide a framework within which to organize a
great deal of descriptive chemistry.
 The intellectual satisfaction derived from constructing models
that accurately reflect the behavior of chemical systems.
 A mechanism is a tool to be used in the search for new
information and new understanding.

Objective: Being able to rationalize reaction outcomes on the

basis of a surprisingly small number of fundamental principles.
 Provide you with the ability to group reactions according to
common mechanisms;
 Predict reaction products for unfamiliar reactions.
A reaction mechanism is a
detailed description of the
bonding changes as a reaction
proceeds. The reaction
mechanism also includes the
many important principles of
organic chemistry. A plausible
mechanism must be consistent
with experimental observations
and the principle of organic
chemistry.
Organic chemists use a
technique called electron
pushing (or called arrow
pushing) to depict the flow or
movement of electrons during
chemical reactions.

DOI: 10.1021/ed500284d
J. Chem. Educ. 2015, 92, 803−810
The Correct Use of Arrows to Indicate Electron
Movement (4 Basic Rules)

First Rule: Arrows are

used to indicate movement
of electrons.

A regular arrow (double-sided arrowhead) is used to indicate the

movement of two electrons, while a line with a single-sided
arrowhead (sometimes called a “fish hook arrow”) is used for
single electron movement involved with radical reactions.
In chemical reactions, both electrons and atoms change positions
as both π and σ bonds are formed and broken. Arrow pushing is
used to keep track of the movement of all electrons involved with
each step of the overall transformation.
Using Arrows in Equations and Rxn Mechanisms
Arrow pushing in resonance contributing
structures is different from that of reaction
mechanisms
Keep in mind that in the case of
resonance,
(1) the atoms do not move between
contributing structures
(2) the electrons are not actually
moving.
The true chemical structure should be
thought of as a hybrid of the
contributing Lewis line structures. It is
worth pointing out that when used with
contributing structures, arrows
generally indicate only the
interconversion of π bonds and lone
pairs (acetate anion) or just π bonds
(benzene), not the formation or
breaking of σ bonds.
Second Rule: Arrows are never used to indicate the
movement of atoms directly.
The arrows only show atom movement indirectly as a consequence
of electron movement when covalent bonds are made and broken.

Correct use of arrows to

indicate electron movement
during a reaction

Incorrect arrow because it is pointing in

the wrong direction! Never use arrows
to indicate atom movement directly
Electron Sources and Sinks: How to Predict What
Will Occur in an Organic Reaction Mechanism
Third Rule: Arrows always start at an electron source
(donor) and end at an electron sink (or acceptor).
An electron source is a bond or a lone pair of electrons. It is most
commonly a π bond or a lone pair on an atom of relatively high electron
density or a σ bond that must break during a reaction. An electron sink is
an atom on a molecule or an ion that can accept a new bond or lone pair
of electrons.
Lone pair to bond: the first example shows the simplified
example of a lone pair on a naked hydroxide ion going to
hydronium ion (“H+”). The arrow shows the formation of a bond
between O and H, with electrons from the lone pair on the oxygen.
Note the changes in formal charge: the “tail” become more
positive, and the “head” becomes more negative.
Bond to lone pair: The second example shows the reverse
reaction: dissociation of water to give H+ and hydroxide ion. Here,
the arrow shows the breaking of the O-H bond, to end up as a
lone pair on oxygen.
Bond to bond: The third example of a bond breaking to form
another bond. Here, the arrow shows the breaking of a π bond
between C1 and C2, and the formation of a new C–H bond
between C1 and H.
Fourth Rule: Bond breaking will occur to avoid
overfilling valence (hypervalence) on an atom serving
as an electron sink.
Considering the arrow used to make
a new σ bond (arrow “a”), the
hydroxide O atom is the electron
source (most negatively charged
atom) and the acetic acid H atom is
the electron sink (atom with highest
partial positive charge). To avoid
overfilling the valence of the H atom
during the reaction the O−H bond of
acetic acid must be broken (arrow
“b”). In so doing, the acetate ion is
formed.

Oxygen with the greatest localized

negative charge, indicated by the most
intense red color;
Electrostatic Acetic acid proton with the largest
molecular surfaces positive charge, indicated by the most
intense blue color
Understanding, as opposed to memorizing,
mechanisms is critical to mastering organic chemistry
The Correct Use of Arrows to Indicate Electron Movement
 First Rule: Arrows are used to indicate movement of electrons.
 Second Rule: Arrows are never used to indicate the movement of
atoms directly. The arrows only show atom movement indirectly as a
consequence of electron movement when covalent bonds are made
and broken.
 Third Rule: Arrows always start at an electron source (donor) and
end at an electron sink (or acceptor).
 Fourth Rule: Bond breaking will occur to avoid overfilling valence
(hypervalence) on an atom serving as an electron sink.

Although the mechanisms you encounter throughout the course may

seem different, they are actually related in fundamental ways. In fact,
almost all of the organic reaction mechanisms you will learn are
composed of only a few different individual elements (steps) that are put
together in various combinations. Your job is to learn these individual
mechanism elements and then understand how to assemble them into
the steps of the correct mechanism for an overall reaction.
Putting it All Together: A Multiple Choice Situation
Fortunately, there are a surprisingly small number of different types
of characteristic mechanism elements (patterns of arrows) to be
considered when trying to predict individual steps of even complex
chemical reactions. For this reason, you should view the prediction
of each step in an organic mechanism as essentially a multiple-
choice situation in which your most common choices are the
following four:
1. Make a new bond between a nucleophile (source for an
arrow) and an electrophile (sink for an arrow): Use this element
when there is a nucleophile present in the solution as well as an
electrophile suitable for reaction to occur.
2. Break a bond so that relatively stable molecules or ions are
created: Use this element when there is no suitable nucleophile-
electrophile or proton transfer reaction but breaking a bond can
create neutral molecules or relatively stable ions or both.

(stabilized by inductive
and hyperconjugation
effects.)
3. Add a proton: Use this element when there is no suitable
nucleophile-electrophile reaction but a strong acid is present or
the molecule has a strongly basic functional group.

4. Take a proton away: Use this element when there is no

suitable nucleophile-electrophile reaction but the molecule has a
strongly acidic proton or a strong base is present.
These four mechanistic elements are the foundation upon
which you will build an understanding of organic reaction
mechanisms.

Properties of such elementary reactions:

 A single transition state;
 Microscopically reversible.

They are far and away the most common; however, they are not
the only mechanistic elements you will see. Once in a while, you
will encounter a reaction with a unique mechanistic element
specific to the particular molecules involved.

When you are able to predict which of the common mechanistic

elements is/are most appropriate for a given step in a mechanism,
you will be able to push electrons correctly without relying on
memorization. Moreover, you will have taken a major
step toward mastering organic chemistry.
 Curly Arrow Formalism and Examples

Curved arrows are also a way of tracking changes in formal charge:

 Since a pair of electrons are being donated from the “tail”, the atom
at this site will have a formal “loss” of one electron, making its
charge more positive by 1.
 Also, since a pair of electrons are being accepted at the “head”, the
atom at this site will have a formal “gain” of one electron, making its
charge more negative by 1.
 Bond Movement, is used to depict synchronous
processes. A Bond Movement arrow starts at a σ
or π bond, and ends at a sextet atom, forming a
new σ or π bond:

It is really shorthand for consecutive or simultaneous bond

breaking and bond making processes:
When a Bond Making or Bond Movement arrow ends
at an octet atom

In this instance, a Bond Breaking or a second Bond

Movement processes has to "clear out" the extra pair of
electron. If this cannot be done in an electronically reasonable
fashion, then the process is not feasible. In this way a series of
electron movements can be strung together. Again, all of the
central carbons have no change in their charges or number of
bonds, except that the first and last atoms change as for Bond
Making and Bond Breaking processes. Note that the last arrow
in a chain must be either a bond making arrow terminating at a
sextet atom, or a bond breaking arrow.
Multiple curly arrows:
No matter how many arrows you draw in sequence, you only ever
change two charges: the initial “tail” and the final “head”.
Multiple curly arrows:
No matter how many arrows you draw in sequence, you only ever
change two charges: the initial “tail” and the final “head”.

Please count the carbon numbers and position very carefully for
long conjugated molecules like this.
 Common problems with electron pushing
1. Watch for violations of the octet rule - always specifically draw
in all of the atoms (including hydrogens and lone pairs) at any
atom undergoing a transformation.

2. Draw arrows in the right direction (from donor to acceptor).

3. Clearly distinguish formal positive charge and electron

deficiency (a sextet atom).

Cationic species like oxonium ions, ammonium ions and the like are usually NOT
electrophilic at the atom bearing the formal positive charge. Each of the species below has
electrophilic properties, but the positively charged O and N atoms are not electrophilic - it is
the atoms attached to O and N that are electrophilic and thus subject to attack by bases and
nucleophiles.
4. The above stricture has to be relaxed for heavier elements like P and
S which are capable of forming compounds that formally violate the
octet rule.

5. Make a clear distinction between formal negative charges and lone

pairs of electrons - they are not always synonymous. For boron and
aluminum ate complexes, there are no lone pairs. Any donor
character arises from the sigma bonds attached to the negatively
charged atom.
6. For delocalized structures, you must pick a specific resonance
structure to do any electron pushing - the "dotted line" formulas and
circle structures for aromatic systems do not work, since bonds and
electron pairs are not shown.

7. Do not combine multiple steps into one long series of arrows. An

experienced chemist may be able to get away with this sort of
behavior, but such mechanisms are confusing and can contain fatal
errors. If a reaction involves a true intermediate, your mechanism
should reflect that.
References and Extra Reading List:
1. Organic Chemistry | 7th Edition, by William H. Brown/Brent L.
Iverson/Eric Anslyn/Christopher S. Foote, Cengage Learning
2013.
2. Molecular Orbitals and Organic Chemical Reactions, Student
Edition, by Ian Fleming, John Wiley & Sons Ltd 2009.
3. https://www.masterorganicchemistry.com/2012/02/15/curved-
arrows-for-reactions/
4. http://ocw.uci.edu/courses/chem_201_organic_reactions_me
chanisms_i.html