Oxidation and Reduction in Organic

Chemistry
oxidation and reduction are two important chemical reactions that occur in organic
chemistry.

Oxidation is the process in which an atom or molecule loses electrons, resulting in an

increase in its oxidation state. This can be achieved by adding oxygen, removing
hydrogen, or removing electrons from a molecule. Oxidation reactions are often
associated with the loss of energy and the production of heat.

Reduction, on the other hand, is the process in which an atom or molecule gains
electrons, resulting in a decrease in its oxidation state. This can be achieved by
adding hydrogen, removing oxygen, or adding electrons to a molecule. Reduction
reactions are often associated with the gain of energy and the production of cold.

In organic chemistry, oxidation and reduction reactions play important roles in many
chemical processes such as metabolism, respiration, and photosynthesis. For
example, during cellular respiration glucose is oxidized to produce energy while
oxygen is reduced to form water.

Overall, oxidation and reduction reactions are fundamental concepts in organic

chemistry that help explain many chemical processes that occur both naturally and
artificially.

Given the decrease in mass, a sensible name for the process was made: reduction.

That was more than 500 years ago.

Later on, Scheele,  Lavoisier and Priestley independently discovered that the loss of
mass was due to the expulsion of an element named (by Lavoisier) oxygen, and
subsequent burning the metal in air led to its recombination.  Hence, “oxidation”.

That was about 200 years ago.

Then came a general understanding of how atoms are composed of a positively

charged nucleus and negatively charged electrons, and the introduction of the
formalism known as the “oxidation state“, which is the hypothetical charge that an
atom would have if all bonds to atoms of different elements of different elements
were 100% ionic. It also works for ions, of course. So here’s the same reaction. See
how oxidation leads to removal of electrons, and reduction leads to a gain of
electrons.

That was about 70 years ago.

This also happens to be the first definition of oxidation and reduction I first learned in
high school. When this was introduced in class, my first question – which is still
asked by many students today, was:

“In what world does it make sense to call a process where electrons are gained
“reduction” ? “

The answer from my high school chemistry teacher was , “well, you’re reducing the
oxidation state – making it more negative”. Which was a very clever answer,
completely jettisoning the inconvenient historical definition in favor of a simplistic
mathematical one. Fortunately for him, I wasn’t fast or clever enough to counter with
“then why isn’t “oxidation” called “addition”? (Feel free to use this yourself,
however).

Result: I just memorized that “reduction” meant “adding electrons” and “oxidation”
meant “removing electrons”.  Which came in handy in general chemistry, with its
seemingly endless balancing of complex redox reactions.

Just when this seemed settled in my mind, along came organic chemistry, with what
was seemingly yet another way of defining oxidation and reduction.  Agh!!!
At first glance, this seems a long way away from the Gen chem definition of oxidation
being loss of electrons and reduction a gain of electrons.

But if you go back to the concept of the oxidation state, it might make some more
sense. If you just pay attention to what’s happening to the oxidation state of the
carbons, you can follow along to see if it’s an oxidation or reduction. If the oxidation
state is becoming more negative, it’s a reduction (gaining electrons). If the oxidation
state is becoming more positive, it’s an oxidation (losing electrons).

Let’s look at those examples again (putting in an extra example for fun), paying
attention to the change in oxidation state.
So is there a quick way to figure out if a carbon is being oxidized or reduced? Why
yes there is.

A reduction will result in a net increase in the number of C-H bonds, or a net
decrease in the number of C-O bonds (or equivalent, such as C-Cl, C-Br, etc).

An oxidation will result in a net decrease in the number of C-H bonds, or a net
increase in the number of C-O bonds (or equivalent). 
All of these events affect the oxidation state of the carbon, and this ties back to the
concept of oxidation that I originally learned in high school: keeping track of the
gaining (and losing) of electrons.

When I finally understood this I was happy to note that the term “oxidation” finally
made sense again.

“Reduction” still didn’t, but I learned to live with it and moved on.  You will too.

Below are a number of common functional group transformations that are classified
as redox.

Heteroatoms such as oxygen and nitrogen are more electronegative than carbon, so
when a carbon atom gains a bond to a heteroatom, it loses electron density and is thus
being oxidized. Conversely, hydrogen is less electronegative than carbon, so when a
carbon gains a bond to a hydrogen, it is gaining electron density, and thus being
reduced.

Exercise 15.2.2

The hydration of an alkene to an alcohol is not classified as a redox reaction.

Explain.
For the most part, when talking about redox reactions in organic chemistry we are
dealing with a small set of very recognizable functional group transformations. The
concept of oxidation state can be useful in this context. When a compound has lots of
carbon-hydrogen bonds, it is said to be in a lower oxidation state, or a more reduced
state. Conversely, if it contains a lot of carbon-heteroatom bonds, it is said to be in a
higher oxidation state.

We'll start with a series of single carbon compounds as an example. Methane, in

which the carbon has four bonds to hydrogen, is the most reduced member of the
group. The compounds become increasingly oxidized as we move from left to right,
with each step gaining a bond to oxygen and losing a bond to hydrogen. Carbon
dioxide, in which all four bonds on the carbon are to oxygen, is in the highest
oxidation state.

More generally, we can rank the oxidation state of common functional groups:

The alkane oxidation state is the most reduced. Alcohols, thiols, amines, and alkenes
are all at the same oxidation state: therefore, a reaction converting one of these groups
to another - an alcohol to alkene conversion, for example - is not a redox reaction.
Aldehydes, however, are at a higher oxidation state than alcohols, so an alcohol to
aldehyde conversion is an oxidation. Likewise, an imine to amine conversion is a
reduction, but an imine to ketone conversion is not a redox reaction.

It is important to keep in mind that oxidation and reduction always occurs in tandem:
when one compound is oxidized, another compound must be reduced. Often, organic
chemists will use the terms oxidizing agent and reducing agent to refer to species that
are commonly used, by human chemists or by nature, to achieve the oxidation or
reduction of a variety of compounds. For example, chromium trioxide (CrO3

) is a laboratory oxidizing agent used by organic chemists to oxidize

a secondary alcohol to a ketone, in the process being reduced to
H2CrO3. Sodium borohydride (NaBH4) is a laboratory reducing agent
used to reduce ketones (or aldehydes) to alcohols, in the process
being oxidized to NaBH3OH

There is a wide selection of oxidizing and reducing agents available for use in the
organic chemistry laboratory, each with its own particular properties and uses. For
example, while sodium borohydride is very useful for reducing aldehyde and ketone
groups to alcohols, it will not reduce esters and other carboxylic acid derivatives. If
you take a course in synthetic organic chemistry, you will learn about the use of many
of these agents.

In this book, of course, we are concerned primarily with the organic chemistry that
occurs within a living cell. A large part of this chapter will be spent looking at the
action of two very important classes of co-enzymes - the nicotinamides and the
flavins - that serve as biochemical oxidizing and reducing agents. We also consider
the oxidation and reduction of sulfur atoms in thiol groups, especially the thiol group
on the side chain of cysteine residues in proteins.

Exercise 15.2.3
Each of the biochemical transformations shown below is a step in amino acid
metabolism. For each, state whether the substrate is being oxidized, reduced,
or neither oxidized nor reduced.

a. (from aromatic amino acid biosynthesis)

a. (from the biosynthesis of arginine and proline)

a. (from the catabolism of lysine)

a. (from the catabolism of tryptophan)

a. (from the catabolism of serine)