Lecture 2

b) Pericyclic Reactions

1. Dihydroxylation Using OsO4, H2O – syn addition. Catalytic conditions using re-oxidant.

2. Ozonolysis Using O3, then (i) Me2S (to produce aldehydes or ketones), (ii) H2O2 (to produce
carboxylic acids), (iii) NaBH4 (to produce alcohols).

Note: Mechanism for the decomposition of ozonide is only required for (i).

3. Hydroboration Using BH3, then alkaline H2O2 – syn addition from less hindered face.
Regiochemistry.

What is a pericyclic reaction ?

Involves a cyclic flow of electrons in the mechanism.

1. Dihydroxylation Using OsO4 (Osmium Tetroxide), H2O (Important) – syn addition. Catalytic
conditions using re-oxidant.

This is a stereospecific reaction – say the 2 OH groups have been added syn to the alkene. Syn
addition of the OH groups

Curly Arrow Mechanism

Osmium is a metal at the bottom of group 8 on the periodic table, so expect its oxides to be ionic but
the oxidation state of osmium is 8 so each oxygen is -2. If it was Os 8 it would be exceptionally
polarising and would be pulling the electron density away from anything even the oxide anion. So
the bond between Os and O are covalent. Because O is very electronegative to has a lot of e density
on it and the Os is also polarising so pulls e density away so shares e density.

Osmium Tetroxide is tetrahedral and physically a slimy solid so if you heat it it will sublime into a
vapour which indicates its more covalent than ionic.
1 and 2 – OsO4 approaches and e density coming from a double bond and finishes in mid air to
indicate e density falls between carbon and oxygen atom

3 – e density from Os=O double bond is ending up on Os bc Os is getting reduced in this process from
+8 to +6

Can isolate an Osmate Ester if you ran this in a complete absence of water that is what you would
end up with. Can grow crystals and solve using X-ray diffraction to solve it. V rare we want the ester ,
so treat reaction with water and the water will hydrolyse the ester. The oxygen lone pair will attack
the Os, its huge so theres plenty of room for that to happen, the water can get in easily, then
protonate the O- you generate, using any acid. H-B is base, not boron. The immediate product of
that process with loss of a proton is that and then a second eq of water will attack Os and nce again
with the loss of a proton you generate your product and this Os by product.

This reactions works really well get 100% yield the problem is that Os is toxic, worse than mercury.
Bc of this run the reaction with sacrificial oxidant to reoxidise Os 6+ back to Os 8+. The product is
with the 2 OH groups added sin.
Reminder – if you wanted the stereoisomer where cyclohexene gave you the trans diol use mCPBA
then open with water, so you would epoxidize is and then open with water, the water would from
the opposite face to which side the epoxide was on and so you get inversion at a second centre you
end up with that.

2. Ozonolysis Using O3, then (i) Me2S (to produce aldehydes or ketones), (ii) H2O2 (to produce
carboxylic acids), (iii) NaBH4 (to produce alcohols).

General reaction scheme

Stereochemistry of the alkene doesn’t matter whether its cis or trans. Going to end up cleaving the
C=C bond entirely, under these conditions where you treat the intermediate that you generate with
dimethyl sulphide, you generate the aldehyde product

Structure of Ozone

Nonlinear, can exist in two canonical forms, resonance, structures, the negative charge is equally
shared between the two oxygen atoms so they carry a partial negative charge whereas the central
oxygen atom carries a formal positive charge.

Mechanism
1 - Electron density flows from the carbon carbon double bond to the oxygen atom which has no
charge then

2 - break the O=O and put that electron density onto the oxygen atom with a formal positive charge

3 – flow of electrons from the negative charge to the carbon carbon double bond

First intermediate, something that has 2 single O-O single bonds which are very weak so this isn’t
stable at all and this immediately rearranges (fragments), gives you 1 eq aldehyde but also 1 eq of
weird molecule got oxygen atom at the end of the aldehyde basically if you rotate one of the
molecules by 180 degrees (aldehyde).

4 - Negative charge is going to be a good nucleophile will attack the electrophilic carbon atom of the
C= carbonyl double bond

5 0 C=O double bond electron density will flow to the Carbon atom on the C-R

6 – then the double bond will break and the e density will flow to the positively charged oxygen
atom

Form a new 5 membered ring now only contains 1 O-O single bond rather than 2, so more stable and
has been isolated (Ozonide)

Ozonide can then be decomposed by treatment with different reagents in the example here we’re
using dimethyl sulphide,

7 – so this is a Nu and the sulphur lone pair is going to attack to try and break the weakest bond
which is the O-O

8 – break the O-O single bond so it forms a C=O with the excess e density , creates a pentavalent
carbon

9 – get rid of the pentavalent carbon by breaking the C-O single bond and forming a second C=O
double bond, again oentavalent carbon forms

10 – these electrons also end up on the oxygen atom

Generates two eq of aldegyde and the by product is di methyl sulphoxide. Electrons are being
donated by the sulfur atoms so it gets a positive charge and the oxygen that has noe arrow leaving
and two arrows going to it measn ti has excess electrons so it has a negative charge.

Insread of Me2S can use :

- H2O2 which gives Carboxylic acids, so you would isolate the acids, not the aldehydes
- NaBH4 (reducing agent) which gives alcohols

3. Hydroboration Using BH3, then alkaline H2O2 – syn addition from less hindered face.
Regiochemistry.

Not always considered a pericyclic reaction

Using methyl cyclopentene, add in effect water across the molecule on the same face of the alkene.
NB: BH3 doesn’t exist at room temperature. Will dimerize to form B2H6. SO organic chemists will
use complexes of BH3 instead

eg. THF

cyclic molecule with an oxygen in it, the oxygen lone pair can donate to the boron to complete the
octet around boron, or di methyl sulphide, Me2S where the sulfur lone pair can donate to the boron
to form a stable complex, then when you run the reaction you usually heat them to break the dative
covalent bond between the ligand and the B of the borane to release borane so that it can then do
the hydroboration reaction.

Mechanism
1 + 2 – BH3 fragments will approach alkene and in effect, that’s what happens. H atoms ends up on
the more hindered more sub carbon and the boron on the less hindered end, this is once again syn
addition from less hindered face

Boron adds to the less sub end of the alkene. 2 reasons for this:

- Boron fragment is bulkier than H so energetically more favourable for it to approach at that
end.
- More favourable charge stabilisation in the transition state.

At the transition state, as those dotted bonds are being broken, and these dotted bonds are being
formed, if you arrange it like so there’s going to be a delta plus growing on that carbon and a delta
minus growing on the boron which is the arrangement of charges you want bc the boron really likes
to have a full octet so you’re going to be pushing electron density on it and the more sub carbon will
be able to stabilise the positive charge better than the less sub carbon. So by bringing the boron in at
that position you’re stabilising the charges better in the transition state.

Back to reaction, that molecule will be able to react with further eq to alkene the boron still has two
BH bonds each of which will continue to react so that you generate (BR2 thing) which is equal to
that.

Can isolate BR2 thing, put want an alcohol group in the product.

Hydrogen peroxide and sodium hydroxide will form an eq where you deprotonate the H2O2 using
the hydroxide anion to generate hydrogen peroxide anion (that’s what acts as a Nu) and

3 - attacks boron, boron is electron deficient when it only has three bonds so it wants to form its 4 th
bond so the immediate product of the reaction is the negative charge on the boron thing. This all
then rearranges

4 - the C-B bond breaks and the electrons from that bond flow to form a bond between the carbon
atom and the oxygen atom as shown

5 – the OH leaves as hydroxide very rare example of hydroxide as leaving group bc breaking O-O
single bond which is v weak

Migration of electrons from C-B bond to C-O bond occurs with retention of configuration, so do not
use the stereochemistry in that step

6 + 7 - Under basic conditions the hydroxide can attack to remove the boron fragment to generate
O- and then protonation gives final product

Regioisomer of the product from the same material

Rather than let the OH add to the less sub carbon, its added to the more sub, can use water with a
bit of acid or you can use mercury acetate and water. Post lecture questions of Lecture 1