Addition Reactions

Course Name: General Chemistry

Course Code: CHEM F111
Lecture Instructor Name: Prof. Subhasish Roy
Department: Chemistry
Email: subhasishr@goa.bits-pilani.ac.in
Chamber No: C 223
Chamber Consultation Hours: Thursday 4:00 PM to 4:50 PM

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Text and Reference Books
Most of the Lecture Slides are
made from the text book. I am
gratefully acknowledging
Solomon’s Organic Chemistry
Book and many other Organic
Chemistry Books.

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Contents
8.2 Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikov’s Rule
8.3 Stereochemistry of the Ionic Addition to an Alkene
8.4 Addition of Water to Alkenes: Acid-Catalyzed Hydration
8.5 Alcohols from Alkenes through Oxymercuration–Demercuration: Markovnikov Addition
8.6 Alcohols from Alkenes through Hydroboration–Oxidation: Anti-Markovnikov Syn Hydration
8.7 Hydroboration: Synthesis of Alkylboranes
8.8 Oxidation and Hydrolysis of Alkylboranes
8.9 Summary of Alkene Hydration Methods
8.10 Protonolysis of Alkylboranes
8.11 Electrophilic Addition of Bromine and Chlorine to Alkenes
8.12 Stereospecific Reactions
8.13 Halohydrin Formation
8.14 Divalent Carbon Compounds: Carbenes
8.15 Oxidation of Alkenes: Syn 1,2-Dihydroxylation
8.16 Oxidative Cleavage of Alkenes

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organic Chemistry
8.2 Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and
Markovnikov’s Rule
Mechanism of the
electrophilic addition of HBr
to 2-methylpropene. The
reaction occurs in two steps,
slow
protonation and bromide
addition, and involves a
carbocation intermediate.

fast

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Solomon’s organic Chemistry
8.2A Theoretical Explanation of Markovnikov’s Rule

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Solomon’s organic Chemistry
8.2B General Statement of Markovnikov’s Rule
➢ In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of
the adding reagent attaches itself to a carbon atom of the double bond so as to yield the
more stable carbocation as an intermediate.
➢ Addition of the electrophile determines the overall orientation of the addition, because it
occurs first (before the addition of the nucleophilic portion of the adding reagent).

Because of the greater electronegativity of

chlorine, the positive portion of this
molecule is iodine.

8.2C Regioselective (Regio comes from the Latin word regionem meaning direction) Reactions
When a reaction that can potentially yield two or more constitutional isomers actually produces only one (or a
predominance of one), the reaction is said to be a regioselective reaction.

The addition of HBr (and other hydrogen halides) is said to be regioselective because in each case, one of the
two possible orientations of addition results preferentially over the other.
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Solomon’s organic Chemistry
8.2C Regioselective Reactions

The following reaction is not regioselective. Because the addition of H+ to either of the sp2 carbons produces a
secondary carbocation, both carbocations are formed at about the same rate. Therefore, approximately equal
amounts of the two alkyl halides are obtained.

This reaction is not Regioselective

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Solomon’s organic Chemistry
8.2C Regioselective Reactions The addition of H+ to 2-hexene forms two different
secondary carbocations. Because the carbocations
have the similar stability, approximately equal
amounts of each are formed. Therefore, half the
product is the desired 3-bromohexane and half is 2-
bromohexane.

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Solomon’s organic Chemistry
8.2D An Exception to Markovnikov’s Rule

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Solomon’s organic Chemistry
Summary of Markovnikov’s Rule

The stereochemistry of the Reaction : Ionic Addition to an Alkene

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Solomon’s organic Chemistry
8.4 Addition of Water to Alkenes: Acid-Catalyzed Hydration

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Solomon’s organic Chemistry
8.4 Addition of Water to Alkenes: Acid-Catalyzed Hydration

8.4B Rearrangements Mechanism

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Solomon’s organic Chemistry
8.5 Alcohols from Alkenes through Oxymercuration (addition of oxygen and
mercury) – Demercuration: Markovnikov Addition

The C–Hg bond is very weak and the

simplest way to replace Hg with H is by
using a reducing agent: NaBH4 works
fine. 13
Solomon’s organic Chemistry
8.5 Alcohols from Alkenes through Oxymercuration– Demercuration:

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8.5 Alcohols from Alkenes through Oxymercuration– Demercuration:

Calculations indicate that mercury-bridged carbocations (termed mercurinium ions) such as those formed in this
reaction Oxymercuration– Demercuration retain much of the positive charge on the mercury moiety. Only a small
portion of the positive charge resides on the more substituted carbon atom. The charge is large enough to account
for the observed Markovnikov addition, but it is too small to allow the usual rapid carbon 15skeleton
rearrangements that take place with more fully developed carbocations.
8.5B Rearrangements Seldom Occur in Oxymercuration–Demercuration
In oxymercuration the mercury
stabilizes the initially formed
carbocation by back-donation of the
mercury d orbitals such that
rearrangement does not occur.
Have a look on previous slide

Solvomercuration–demercuration

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Solomon’s organic Chemistry
⌂ Oxymercuration–Demercuration Consequences: summary
Although attack by water on the bridged mercurinium ion leads to anti addition of the hydroxyl
and mercury groups, the reaction that replaces mercury with hydrogen is not stereocontrolled (it
likely involves radicals). This step scrambles the overall stereochemistry.

∑ The net result of oxymercuration–demercuration is a mixture of syn and anti addition of -H

and -OH to the alkene.
∑ As already noted, oxymercuration–demercuration takes place with Markovnikov
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regiochemistry.
8.6 Alcohols from Alkenes through Hydroboration– Oxidation: Anti-
Markovnikov Syn Hydration
Anti-Markovnikov hydration of a double bond can be achieved through the use of diborane (B2H6) or a solution
of borane in tetrahydrofuran (BH3:THF).

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Solomon’s organic Chemistry
8.7 Hydroboration: Synthesis of Alkylboranes

8.7A Mechanism of Hydroboration

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Solomon’s organic Chemistry
8.7 Hydroboration: Mechanism
Hydroboration was discovered by
Herbert C. Brown (Purdue
University)

Stereochemistry of the addition

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Solomon’s organic Chemistry
8.7B Stereochemistry of Hydroboration: anti-Markovnikov addition

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Solomon’s organic Chemistry
8.7B Stereochemistry of Hydroboration

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Solomon’s organic Chemistry
8.8 Oxidation and Hydrolysis of Alkylboranes
Mechanism

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Solomon’s organic Chemistry
8.8 Oxidation and Hydrolysis of Alkylboranes
Mechanism

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Solomon’s organic Chemistry
Mechanism to show both –H and –OH stays cis to each other (either at
wedge or dash) in Hydroboration followed by oxidation

Now we can prove that cis addition really does occur in the hydroboration step. The migration
of carbon from boron to oxygen might remind you of the Baeyer–Villiger rearrangement. Both
these rearrangements occur with retention of configuration at the migrating group as the
bonding (C–C or C–B σ) orbital reacts. Here is the exact analogy.

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Clayden’s organic Chemistry
Hydroboration summary

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Clayden’s organic Chemistry
8.9 Summary of Alkene Hydration Methods

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Solomon’s organic Chemistry
8.10 Protonolysis of Alkylboranes

Assuming you also have available

BD3:THF and CH3CO2T, can you
suggest a synthesis of the following
?

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Solomon’s organic Chemistry
8.11 Electrophilic Addition of Bromine and Chlorine to Alkenes

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Solomon’s organic Chemistry
8.11 Electrophilic Addition of Bromine and Chlorine to Alkenes

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Solomon’s organic Chemistry
8.12 Stereospecific Reactions
❑ The anti addition of a halogen to an alkene provides us with an example of what is called a stereospecific
reaction.
❑ A stereospecific reaction is one where a particular stereoisomer of the starting material yields a specific
stereoisomeric form of the product.

The reactants cis-2-butene and trans-2-

butene are stereoisomers; they are
diastereomers. The product of reaction 1,
(2R,3S )-2,3-dibromobutane, is a meso
compound, and it is a stereoisomer of both
of the products of reaction 2 (the
enantiomeric 2,3-dibromobutanes). Thus,
by definition, both reactions are
stereospecific. One stereoisomeric form of
the reactant (e.g., trans-2-butene) gives
one product (the meso compound),
whereas the other stereoisomeric form of
the reactant (cis-2-butene) gives a
stereoisomerically different product (the
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enantiomers). Solomon’s organic Chemistry
8.12 Stereospecific Reaction’s Mechanism

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Solomon’s organic Chemistry
8.12 Stereospecific Reaction’s Mechanism…

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Solomon’s organic Chemistry
Halohydrin Formation from an Alkene

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Solomon’s organic Chemistry
Stereospecific Reaction’s Mechanism & Bridge bromonium ion

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Solomon’s organic Chemistry
Stereospecific Reaction’s Mechanism…
Write a mechanism to explain the following reaction.

If the alkene is unsymmetrical, the halogen ends up on the

carbon atom with the greater number of hydrogen atoms.

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Solomon’s organic Chemistry
8.14 Divalent Carbon Compounds: Carbenes
❑ Methylene (:CH2) is the simplest of the carbenes: uncharged, reactive intermediates that have a carbon atom
with two bonds and two nonbonding electrons.
❑ Like borane (BH3), methylene is a potent electrophile because it has an unfilled octet. It adds to the electron-
rich pi bond of an alkene to form a cyclopropane.

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Solomon’s organic Chemistry
8.14B Reactions of Other Carbenes: Dihalocarbenes

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8.14C Carbenoids: The Simmons–Smith Cyclopropane Synthesis
▪ A useful cyclopropane synthesis was developed by H. E. Simmons and R. D. Smith of the DuPont Company.
▪ In this synthesis diiodomethane and a zinc–copper couple are stirred together with an alkene.
▪ The diiodomethane and zinc react to produce a carbene-like species called a carbenoid:

▪ Stereospecific
carbene addition

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Solomon’s organic Chemistry
8.15 Oxidation of Alkenes: Syn 1,2-Dihydroxylation
❑ Osmium tetroxide is widely used to synthesize 1,2-diols (the products of 1,2- dihydroxylation, sometimes
also called glycols).
❑ Potassium permanganate can also be used, although because it is a stronger oxidizing agent it is prone to
cleave the diol through further oxidation.

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Solomon’s organic Chemistry
8.15 Oxidation of Alkenes: Syn 1,2-Dihydroxylation

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8.16 Oxidative Cleavage of Alkenes
❑ Alkenes can be oxidatively cleaved using potassium permanganate or ozone (as well as by other reagents).
Potassium permanganate (KMnO4) is used when strong oxidation is needed. Ozone (O3) is used when mild
oxidation is desired.
8.16A Cleavage with Hot Basic Potassium Permanganate
✓ Treatment with hot basic potassium permanganate oxidatively cleaves the double bond of an alkene.
✓ Cleavage is believed to occur via a cyclic intermediate similar to the one formed with osmium tetroxide and
intermediate formation of a 1,2-diol.
✓ Alkenes with monosubstituted carbon atoms are oxidatively cleaved to salts of carboxylic acids.
✓ Disubstituted alkene carbons are oxidatively cleaved to ketones.
✓ Unsubstituted alkene carbons are oxidized to carbon dioxide.
8.16 Potassium permanganate oxidative cleavage of the double bond
of an alkene: Mechanism

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8.16B Cleavage with Ozone
8.16B Cleavage with Ozone: Mechanism
8.16B Ozonolysis: Mechanism Relook

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8.16B Ozonolysis: Few Examples

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Insertion of oxygen in alkene: Epoxidation by peracids

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∑ Addition
Reactions
Summary
∑ Addition Reactions Summary
∑ Addition Reactions Summary
∑ Addition
Reactions
Summary
Electrophilic
Addition of
Bromine
and Chlorine
to Alkynes: Not
in your syllabus

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