Arrow-Pushing and Solving Mechanism Problems

A. General Points:
1. It is important that you understand exactly what the various arrows represent:

flow of two electrons

flow of one electron

reaction arrow

equilibrium arrow

resonance arrow

retrosynthetic arrow

2. Why curved arrows?

(a) One curved arrow = two electrons = one bond (when a bond is being formed or broken) or one
lone pair of electrons.
(b) The arrow starts where the two electrons originate, and points toward the atom with which the
electrons are reacting or end up on (this means that an arrow can never start at H+).
Example 1

Example 2
O

Et3N

Et3N H

H Cl

Cl

H3 C

O
OH

H3 C

H2 O

B. Specific Tactics and Hints:

Example 3
H3C

H3C

cat OH

OH

OH
O

H3CO OH

1. Draw out the starting materials, reagents, and products as clear structures, including formal charges
and lone pairs.
2. Compare the starting material(s) and product(s).
(a) Count the atoms in the starting material(s) and product(s). Determine what is lost or gained. This
helps you keep track of all the atoms in the reaction. Moreover, it may give you a hint as to what
type of reaction occurs. For Example 3, the starting material has 7 carbons, 3 oxygens, and 16
hydrogens. The product has 6 carbons, 2 oxygens, and 12 hydrogens. This tells you that you are
losing 3 carbons, 1 oxygen, and 4 hydrogens you might recognize that this is H3COH
(methanol).
H3C
H3CO OH

OH

cat OH

H3C

OH
O

H3COH

(b) Determine which bonds are formed and which are broken. Doing so gives you an idea of what
reactions might occur. For Example 3, in order to form a cyclic structure a new C-O bond must be
formed as indicated in the product. We also have identified that the starting material loses
methanol, thus the C-OMe bond probably breaks.
H3C

cat OH

H3C

OH
+

H3CO OH

H3COH

(c) Determine which pieces of the product(s) correspond to which part of the starting materials. In
Example 3, it is most likely that the methanol comes from the OCH3 group in the starting material
as we have highlighted in blue.
H3C

cat OH

H3C

OH
+

H3CO OH

H3COH

(d) Determine which pieces of your starting material(s) are lost and what remains unchanged. We
have already identified that we lose methanol. We can also see that the carbon indicated by an
asterisk (*) forms a new bond to the alcohol (*).
H3C

OH

cat OH

H3C

OH
*

H3CO OH

O*

H3COH

(e) Number the atoms. This exercise may help you if the starting materials and products look
drastically different. First, assign each atom in the starting material a number, especially the
carbon atoms. Next, try to match up one or two key atoms in the starting material with their
counterparts in the product(s), and give them the same numbers. For example, there is only one
methyl group in our starting material and product so we can guess that this is the same carbon #1
in both product and starting material as assigned below.
1
3
5
4
H3C 2
6 OH
H3CO OH
7

cat OH

1
H3C 2 OH
3
O
6

H3COH
7

3. Consider the reaction conditions and how the starting materials are affected by them. Ask what do
these kinds of molecules do? For example, what are the nucleophilic and electrophilic sites of my
starting materials? Or under acidic conditions, what is the most basic site of my starting material? In
Example 3, you might recognize that the starting material is a hemiacetal. Under basic conditions,
hemiacetals are in equilibrium with a carbonyl and an alcohol. Also, since the reaction is under basic
conditions, it is likely that something will get deprotonated. The two alcohol protons are the most
acidic protons in the starting material so these are likely candidates.
4. Start pushing arrows. In our analysis of Example 3, we suggested that deprotonation of one of the
alcohols would be a reasonable first step under basic conditions. We also recognized that our starting
material contains a hemiacetal. It therefore might make sense to begin by deprotonating the hydroxyl

group of the hemiacetal. This generates water and an alkoxide. Since we need to lose CH3OH, we can
now do that by having the lone pair on the alkoxide add to the hemiacetal carbon, breaking the COCH3 bond and placing the electrons from the breaking bond on oxygen. We have produced a ketone
intermediate that has the exact same number of carbons, hydrogens, and oxygens as the desired
product. From here, the mechanism for product formation should be recognizable. Intramolecular
(within the same molecule) hemiacetal formation leads to product as shown below.

H3C

OH

H3CO O
H

OH

OH

H3C

H3C

OCH3

H3CO O
+ H2O

OH

H3C OH

O
H3C O

H OH

H3C

+ H3COH

(a) REMEMBER: write out every step of the mechanism and every intermediate.
(b) It can help to draw your starting material in a similar orientation to your product.
(c) Reevaluate your mechanism at intermediate stages to assess whether you are making productive
changes (i.e. getting closer to the structure of the product).
(d) If you get stuck, analyze your intermediates in the mechanism as you did for the starting material
in part 2
5. Double check your mechanism:
(a) Do not invoke strongly basic intermediates under acidic conditions. Do not invoke strongly acidic
intermediates under basic conditions. For Example 3, you should not generate + charges on any of
the intermediates.
(b) The net charge in the overall system must be conserved from starting material(s) to product(s).
(c) Check the numbering of carbon atoms in the starting material and product and determine if it is
consistent with your arrow-pushing.
(d) Carbon should never have more than 8 valence electrons. In general watch out for the octet rule
(it helps to draw out all implicit hydrogens at the reaction site(s)).

Arrow Pushing Exercises

1

OH

H3C

OH

H3C

H2O

2
Br
Br
3

CH3
CH3
H3C
Cl

Br

H
H

CH3
H3C

Cl

CH3

H2O

H2C CH2

OH

Br

Br

CH3
CH3

CH3

OH

Br

CH2

CH3

H3C

Ph

O Li

Li CH3

CH3
CH3

8
H3C

CH3

O OCH3

OCH3

HO OH
H3C

H3C

CH3

O
CH3

Ph

HO OPh
CH3

12

O
OH

CH3

H OH2

Li

Ph

Me2CuLi
CH3

Li
CH3

H
HO OPh
H3C
Li

O
H

H3C

Al
H

H3C

CH3

H3C
H

10

H3C

CH3

11

CH3

H2O

AlH3

H3C

CH3

PhOH
CH3

H2O

H
H3C

CH3

CH3

H
H3C

CH3

Mechanism Problems

OH

1.

2.

HO

OH

H+, CH3OH
H3CO

OH

pH 7

HO

OH

OH
OH

OH
+

O
3.

O
O

O
HO

OH

OH

OH (cat)

OH

4.

OH
5.

OH
O

NaBH4, MeOH
OH