Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof.

Robert Batey, Page 1

Understanding Organic Reactions

Electron-Pushing or Arrow-Pushing
• Pictoral depiction of a reaction mechanism showing changes in bonding.
• Shows how electrons "move" in the conversion of reactant(s) to product(s),
specifically how bonding pairs of electrons (i.e., covalent chemical bonds) and
lone-pairs of electrons change.
• Movement of 2-electrons is depicted by a curved single-headed arrow.
These arrows show the making and breaking of bonds.

"tail" of arrow "head" of arrow

electrons emanate from a "source"
i.e., from a non-bonded lone pair of
electrons or from a σ or a π-bond
electrons "flow" in this driection toward
an electron "sink"
i.e., toward an atom or bond that can
accept an electron pair, such as a σ*
or p* molecular orbital or an empty
atomic orbital (e.g. d-orbital)

Example: the SN2 Reaction - Anatomy of an "Electron-pushing" Mechanism

electrons "flow" from a non-
bonded pair of electrons on the species bears a
the oxygen atom, toward the formal -ve charge
electrophilic C-atom, making
a new C–O σ-bond the dotted line depicts a the double dagger depicts a
partial bond transition state
H H
H H H H
H C C H
C H
SN2
H O C Cl HO C Cl HO C Cl
H H
H H H H
reactants transition state products
reaction arrow
electrons simultaneously
"flow" toward the Cl atom,
breaking the C–Cl σ-bond

In many cases we abbreviate the structures and mechanism, by (i) not showing a transition state,
(ii) not showing all C–H bonds, and (iii) not showing all or any of the lone-pairs of electrons. Thus
the mechanism shown above can be redrawn as:

HO SN2
OH Cl
Cl
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 2

Understanding Organic Reactions

Electron-Pushing or Arrow-Pushing
Most organic reactions involve those between a nucleophile and an electrophile, in which
just one new sigma-bond is formed. There are two notable exceptions, (i) free-radical
reactions, and (ii) pericyclic reactions. We will see a few examples of these reactions later
in the course. Nevertheless, the vast majoirty of reactions that you will see involve
nucleophile - electrophile reactions.

In many mechansims more than one curved arrow is shown for a step of a reaction. The
curved arrow which shows the new sigma-bond being formed can be used to identify which
component is the nucleophile and which is the electrophile. Considering the case of a
nucleophilic displacement (SN2 reaction) shown again below. Here the oxygen atom of the
hydroxide anion is the nucleophilic atom, whereas the C of the C–Cl bond is the
electrophilic atom. We say that the hydroxide is the nucleophile (the electron pair donor)
and the chloroethane is the electrophile (the electron-pair acceptor)
electron movement showing a
electron movement bond being broken
showing a bond
being made
HO SN2
OH Cl
Cl

nucleophilic
centre electrophilic
centre

Now consider the more complex mechanisms shown below:

electron movement showing a

new sigma bond being made

N O N O

OCH3 OCH3
nucleophilic
centre
electrophilic
centre

electron movement showing a

new sigma bond being made

O
O
C Br Br
H3C CH2 C Br Br
H3C C
H H
nucleophilic electrophilic
centre centre
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 3

Understanding Organic Reactions

Electron-Pushing or Arrow-Pushing

We should carefully distinguish the various arrow types we use in organic chemistry:

reaction arrow

electron-push depicting
or equlibrium arrow involvement of 2-electrons

fishhook arrow:
resonance arrow electron-push depicting
involvement of 1-electron
(note the head of the arrow
only has one hook)

retrosynthetic arrow

It is essential that you show the correct arrows when you draw reactions/mechanisms!
If you use the wrong arrow, it shows an improper understanding of organic chemistry
(you will lose points on an exam).

For example what is wrong with the following scheme?

O O

N N

The electron pushcing is correct, as are the two structures! What then is the problem?

The arrow interconnecting the two structures is a "reaction arrow", whereas the two structureas are in fact
resonance structures. Therefore a "resonance arrow" should be depicted.

You may be asking why is this a problem? As shown the reaction arrow depicts a reaction in which the two
structures represent physically distinct species. This is not the case here, since the two "structures" show
resonance (the atoms have not changed positions), i.e., the true structure is a hybrid of these structures. (Again
it is worth emphasizing that resonance is also not an equilibrium.)
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 4

Classes of Electron "Sources":

1. Non-bonded lone-pairs of electrons on heteroatoms and carbanions, e.g.
R
H2O R3N RO RS C O N C R C C
R

e.g.
SN2
HS O O
HS

Note: it is common to omit drawing lone-pairs that are not directly involved in a reaction. However, you
must always draw lone-pairs that are used as "sources" for your electron-flow mechanisms. For
example, in the mechanism shown above, only one lone-pair is shown on sulfur in the reactant,
whereas in fact there are three lone-pairs on sulfur in HS–. Also, there are no lone pairs drawn on the
oxygen of the second reactant, or on either of the sulfur or oxygen atoms of the product (in fact there
are 2, 2 and 3 lone pairs on these atoms, respectively).

2. Electron-pair from π-bonds, e.g.

paritcularly electron-rich
π-bonds, e.g.
C C
O R2N

alkenes aromatics alkynes dienes

H Br H
e.g.
H H Note: it is common to omit drawing eithercarbon
atoms or the H-atoms on a C–H bond. However, it is
Br often useful to draw in the H atoms that are involved
or are close to the reacting centres.

3. Electron-pair from electon-rich or strained σ-bonds, e.g.

H
δ– δ+ δ– δ+
R Li R MgCl H Al H cyclopropanes

O
e.g.
H H H3C O Li
Li
CH3 H H
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 5

Classes of Electron "Sinks":

1. Acidic hydrogen atoms, usually X–H (X=heteroatom) but sometimes C–H bonds, e.g.

H O H O H O
H O R H
H O R N R S O H C C H
H O H O

e.g.
O H H O H H
H O H + O
R H H R H H

2. Species with unfilled orbitals (i.e., Lewis acids) - usually p- or d-orbitals, e.g.

F O
M F B C Si Cl P Cl
R
F RO

BF3 BF3
e.g. O O
C C
H H H H

3. Carbon atoms in π-bonds, usually polarized such as C=O or C=N (less

commonly C=C), e.g.

O O NH
C O
C C C C C
R R R Cl R H

e.g.
O HO O

HO C C
R OCH3 R OCH3
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 6

Classes of Electron "Sinks":

4. Carbon atoms in polarized σ-bonds C–X (X=heteroatom), e.g.

R R R H
C Cl C OSO2R' C O
H H H H H H H

e.g.
H H H H
H N C Cl H N C H Cl
H H H H H

5. Heteroatoms in polarized σ-bonds X–Y (X and Y=heteroatoms), e.g.

R R
Br Br I I O O S S
R R

Note: such σ-bonds between two heteroatoms are usually quite weak.

H
e.g.
Br Br Br
Br
H
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 7

10 Basic Rules of Electron-Pushing:

1. Octet Rule: for first row elements (i.e., C, N, O, F) make sure the octet rule is obeyed. Not obeying the octet
rule is a common error. Elements in lower rows of the periodic table also often obey the octet rule, but there
are many examples that do not. For example, there are many examples of molecules where P and S obey the
octet rule, but others do not, e.g., O=PCl3 can be considered to have 10 electrons around the phosporus atom.
This is often rationalized by invoking the use of d-orbitals to accept the additional electrons.

2. Conservation of Charge: the overall combined charge of the reactants should be the same as that for the
products. It is a common error to see mechanisms in which the total charge changes.

3. Fomal Charges : ensure that you write correct formal charges for atoms. Also, a common error.

4. Lone Pairs: Similarly draw all relevant non-bonded lone-pairs of electrons.

5. Conservation of Atoms (Matter): ensure that you do not add or lose atoms into your products that were
not present in the reactants. This is a remarkably common error, particularly adding or losing H-atoms present
as C–H bonds, or adding and removing carbon atoms.

6. Direction of Electron "Flow": electrons "flow" from electron-rich sites to electron-poor sites. Not the other
way around! Indicating electrons flowing in the wrong "direction" is a very common error, therefore, be careful
to avoid pushing electrons in the wrong direction.

7. Positioning of Electron-Flow Arrows: it is important to show the electron-flow arrows at the corrrect
positions relative to the bonds in the reactants. This is a common error.

8. Positioning of Atoms: ensure that the connectivity of the atoms in reactants and products is correctly
drawn. It is common to see atoms or groups being drawn at the wrong positions in molecules.

9. Show all of the Electon-Flow Arrows: it is common to see mechanisms drawn that have missed out one
or more of the electon-flow arrows.

10. Do not combine electon-flow arrows for multiple steps as if they were occuring as a single step: it
can be tempting to draw a reactions mechanism as occurring as a single step, even though the reaction takes
place via two or more discrete steps. In some cases such mechanisms do not make "chemical sense",
whereas in others, although such a mechanism may appear reasonable, experimental evidence may indicate
multiple steps. This is another very common error.

Finally, one additional "rule" ....

11. Stongly Acidic / Basic Conditions: another very common "mistake" is to show a mechanism that shows
both strong acids and bases as coexisting under the same reaction conditions. This is not strictly an electron-
pushing error, but it is useful to include here, since it is a very common error.

Often incorrectly drawn mechanisms/reactants/products combine multiple errors.

In the following examples, comparisons of incorrectly and correctly drawn mechanisms are
depicted. Identify the problems with the incorrect mechanisms.
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 8

Mechanisms: Examples of Incorrectly Drawn Products

N H
+ H2O incorrect

O
O

N H
H O N H incorrect
+ H2O
H

N H
+ H2O correct

O
N incorrect
C

O
N C

CH3

N
C correct

O
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 9

Mechanisms: Examples of Incorrectly

Drawn Electron-Flow Arrows

O
O Li+

H H incorrect
H H H

Li H

O
O Li+

H H incorrect
H H

H H
Li

O
O Li+

H H correct
H H
H H
Li

F
F OH
H HO
H
incorrect

F
F OH
H OH
H
correct
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 10

Mechanisms: Examples of Incorrectly Drawn

Electron-Flow Arrows

N
N
incorrect
H H
H H
O
O H3C H
H3C H

N
N

H H
H H
O
O H3C H
H3C H

HO H Br H H
H H
Br H2O incorrect

HO H Br H H
H H
Br H2O correct
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 11

Mechanisms: Examples of Violations of the Octet Rule

H3C
O CH3
CH3
H O O CH3
H O
incorrect
H H
H H

CH3
O CH3
O
correct
H H
H H
O
O H3C H
H3C H

O O
Li
H
H Li
H
H incorrect

H
H H O Li
Li
O
H
correct
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 12

Questions: Identify the Mistakes of the

Following Reaction Mechanisms

H Br
H

(a) H Br

Li Li
O O
(b) C C
H3C H H3C H

H O H O
(c) N N
H O H O

(d)
Cl H2O Cl
HO H

CH3
HO CH3
HO
(e) C CH3
H3C CH3 CH3

(f)
P O P O
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 13

Questions: Predict the Products of the

Following Reactions

(a) O
N C

O
O O

(b)

O N

H
(c) H

O
H3C
Cl
H
(d) H

N
R R
R

O R

Se
O
(e)

H
 Organic Chemistry, Basics of Arrow/Electron Pushing Mechanisms, Prof. Robert Batey, Page 14

Questions: Show the Electron Flow Arrows in

the Following Reactions

(a) N
N C C
Br

O N O O
(b)
H N O
H

– H+

O O
N

(c) R O R O
R R
P P
R CH2 R C H
H H H2 H

R O R
P R O
R H P
R R
C H
H
H H2 H