PAPER OF ORGANIC CHEMISTRY

OXIDATIOIN OF ALKENES
( Responsibility Lecturer: Dr. Netti Herawati, S.Pd., M.Si )

Arranged by:

Name : St. Anisa

ID Student : 220105510003

ICP OF CHEMISTRY EDUCATION

CHEMISTRY DAPARTMENT

MATH AND SCIENCE FACULTY

MAKASSAR STATE UNIVERSITY

MARCH 2023

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 ALKENES: OXIDATION AND CLEAVAGE REACTIONS

Sourse: https://www.masterorganicchemistry.com/2011/11/01/introduction-to-
oxidative-cleavage-reactions/

The four posts on acid-base, substitution, addition, and elimination covered the 4

main reactions in organic chemistry I. In this second series of posts we go beyond these
to introduce a few of the less common (but still important) reactions you learn in
organic chemistry 1. We’ve talked about rearrangements and free-radical substitution:
we finish up here with lots of  cleavage (oxidative cleavage).
As I’ve said with everything in this series, the point is not to
understand why just yet, but to be able to see from the diagrams what bonds are broken
and formed. You need to understand how to read  line diagrams and also the concept
of isomers. But other than that no further skills are required. The point here is to be able
to follow the plot – to see what is happening. A later series of posts will go into more
detail as to why things happen.
So what do I mean by “oxidative cleavage reactions”.
When certain types of compounds: [1,2-diols (vicinal diols), alkenes,
and alkynes], are treated with certain reagents, carbon-carbon bonds are cleaved, and
carbon oxygen bonds are formed. When we increase the number of C-O bonds at the
expense of C-C or C-H bonds, that’s referred to as “oxidation“.
Let’s have a look at diols (carbons with alcohols on adjacent carbons). When
diols are treated with NaIO4 (sodium periodate), the carbon-carbon bond between the
two diols is cleaved, and we form two new carbon-oxygen double bonds. This can give
us either aldehydes or ketones, depending on what our starting diol looks like.
Note the pattern: break C–C, form C–O.

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Here’s a different oxidative cleavage reaction using our friend from the upper
atmosphere, ozone (O3). Treatment of an alkene with ozone results in cleavage of the
carbon-carbon double bond, and formation of two new carbon-oxygen double bonds.
It’s like you take a pair of scissors and cut the bond in half, and cap each half with an
oxygen. It’s not a good time here to explain the purpose of O 3 or why it does what it
does or why the Zn is important (plug: they’re in the Reagent Guide) but they all have
their purpose.
Note that again, aldehydes or ketones are formed, depending on the pattern of the diol
we start with. And if we start with alkynes, we end up cleaving all three C-C bonds and
obtain carboxylic acids.

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Here’s the final example. Some reagents will not only oxidize C-C bonds, but they will
oxidize C-H bonds too. In particular, ozone – when treated with hydrogen peroxide –
does this, and so does KMnO4 (potassium permanganate). In both cases we end up with
carboxylic acids instead of aldehydes. Note that if we don’t have any hydrogens
attached to the alkene carbon, we still end up with a ketone.

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One of the frustrating things about these reactions is that it’s really hard to explain
exactly WHY these reagents work the way they do, and HOW it came to be that we use
*these* reagents, and not others. The cold, unsatisfying truth is that organic chemistry is
very much an experimental science, and long ago it was found that these reagents just
work really well at doing these reactions. A deep understanding of exactly *why* and
*how* these reagents worked the way they do came much later, and is sadly, beyond
the scope of your standard introductory course. This is part of the reason why I found
introductory organic chemistry extremely frustrating. Asking your introductory organic
instructor about why these reagents work is like a 7-year old asking their mom about
where babies come from. You get nothing but lies and half truths because they’ve
decided you’re not ready for that information yet.

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 OXIDATION REACTION OF ALKENES

Source: https://batch.libretexts.org/print/url=https://chem.libretexts.org/Bookshelves/
Organic_Chemistry/Organic_Chemistry_I_(Liu)/10%3A_Alkenes_and_Alkynes/
10.07%3A_Oxidation_Reactions_of_Alkenes.pdf

lkenes undergo a number of reactions in which the C=C double bond is oxidized.
For organic compounds, a conventional way to tell whether the oxidation or reduction
occur is to check the number of C–O bonds or the C–H bonds. An oxidation
reaction increase the number of C–O bonds or decrease the number of C–H bonds. On
the other side a reduction reaction increase the number of C–H bonds or decrease the
number of C–O bonds. The relative oxidation state of some common organic functional
groups are listed here based on the trend.

Figure 10.7a The relative oxidation state of some common organic functional groups

10.7.1 Syn 1,2-Dihydroxylation

1,2-Dihydroxylation, the conversion of the C=C double bond to 1,2-diol, is an

oxidative addition reaction of alkene. Osmium tetroxide (OsO 4) is a widely used
oxidizing agent for such purpose. Potassium permanganate can be used as well,
although further oxidation is prone to occur to cleave the diol because it is a stronger
oxidizing agent (10.7.2).

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 Figure 10.7b Example of 1,2-Dihydroxylation

The traditional method of 1,2-dihydroxylation with osmium tetroxide is a two-

step procedure. Osmium tetroxide first reacts with alkene to from a cyclic osmate ester
intermediate and this cyclic intermediate involves the syn addition of OsO4 to the
double bond. The cleavage of the O—Os bond of the intermediate then take places in
the second step with reducing agent NaHSO3, without modifying the stereochemistry of
the C—O bond. The diol formed therefore has the syn stereochemistry property.

Figure 10.7c 1,2-dihydroxylation mechanism

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Catalytic OsO4 1,2-Dihydroxylation

The 1,2-dihydroxylation with osmium tetroxide an effective reaction that used

very often in the labs for the preparing diol from alkene. However, this method has
major drawbacks because osmium tetroxide is a highly toxic, volatile and expensive
reagent. Improved methods have been developed that allow only catalytical amount of
OsO4 being used in conjunction with a co-oxidant in stoichiometric amount. N-
methylmorpholine N-oxide (NMO) is one of the most commonly employed co-oxidants.
In such condition, osmium compounds are re-oxidized by NMO and can be reused to
react with more alkenes, so only small molar percentage of OsO 4 is necessary in the
reaction mixture. The reaction proceeds smoothly with syn diols produced in good
yield.

Figure 10.7d Example of a Catalytic OsO4 1,2-Dihydroxylation

In terms of the stereochemistry of the product, although the syn addition could
occur on either side of the alkene plane, that gives the same product which is the meso
compound. This can be identified by either looking for the plane of symmetry of the
product, or by assigning the absolute configuration on the chirality centers. Review the
stereochemistry knowledge.