Alkene Reaction Guide

Addition of Hydrochloric Acid (HCl)

Description: Treatment of alkenes with hydrochloric acid (HCl) will result in
the formation of alkyl chlorides. The chlorine always ends up at the more
substituted carbon of the alkene, since protonation of the alkene will result in
the more stable carbocation.

Notes: Note that this reaction is Markovnikoff selective. Since it goes

through a carbocation, rearrangements are possible.
Examples:

Notes: When a secondary carbocation is formed adjacent to a tertiary or

quaternary carbon, rearrangements are possible. Note the third example
where Markovnikoffs rule gives no clear preference a mixture will be
obtained.
Mechanism: Electrons from the C1-C2 bond attack the hydrogen of HCl,
expelling the Cl anion and leading to the formation of a carbocation (Step 1,
arrows A and B). Note that the most stable carbocation is formed
preferentially. The chloride anion then attacks the carbocation, leading to
formation of the alkyl chloride (Step 2, arrow C).

Addition of HBr to Alkenes

Description: Treatment of alkenes with hydrobromic acid will result in the

formation of alkyl bromides.
Notes: This is an addition reaction. Note that the bromine always ends up at
the more substituted carbon of the alkene (Markovnikoff-selectivity)
Examples:

Notes: When a secondary carbocation is formed adjacent to a tertiary or

quaternary carbon, rearrangements are possible. Note the third example
where Markovnikoffs rule gives no clear preference, a mixture will be
obtained. Note that the right hand molecule of the third example contains a
stereocenter, which will be obtained as a racemic mixture (1:1 mixture of
enantiomers).
Mechanism: Electrons from the C1-C2 bond attack the hydrogen of HBr,
expelling the bromide anion and leading to the formation of a carbocation
(Step 1, arrows A and B). Note here that the carbocation preferentially forms
on C2 (secondary) and not C1 (primary) since secondary carbocations are
more stable. The bromide anion then attacks the carbocation, leading to
formation of the alkyl bromide (Step 2, arrow C)

Notes: Since the carbocation is planar (flat) there is no preferred direction of

attack of the bromide ion. If its possible to form a stereocenter, a mixture of
stereoisomers will be obtained.

Additional example (advanced) : If the molecule contains adjacent

stereocenters, the two directions of attack on the carbocation will no longer
be of equal energy and a mixture of diastereomers will be obtained. In this
example, attack of the bromide ion on the less hindered top face of the
carbocation is favored, and a mixture of products (diastereomers) will be
obtained.

Addition of Hydroiodic Acid (HI)

Description: Treatment of alkenes with hydroiodic acid (HI) leads to the
formation of alkyl iodides. Note that the iodine always ends up on the more
substituted carbon.

Notes: Note that this reaction is Markovnikoff selective. Since it goes

through a carbocation, rearrangements are possible in some situations.
Examples:

Notes: When a secondary carbocation is formed adjacent to a tertiary or

quaternary carbon, rearrangements are possible. Note the third example
where Markovnikoffs rule gives no clear preference a mixture will be
obtained.
Mechanism: Electrons from the C1-C2 bond attack the hydrogen of HI,
expelling the iodide ion and leading to the formation of a carbocation (Step
1, arrows A and B). Note that the most stable carbocation is formed
preferentially. The iodide anion then attacks the carbocation, leading to
formation of the alkyl iodide (Step 2, arrow C).

Alcohols from Alkenes (H3O+)

Description: Addition of aqueous acid to alkenes leads to the formation of
alcohols.

Notes: Note that the alcohol is formed at the most substituted carbon of the
alkene (Markovnikoff selectivity!) Since this reaction proceeds through a
carbocation, rearrangements can occur in some cases.
Aqueous acid is often written as H3O(+) . An alternative way to depict
aqueous acid is H2O/H2SO4. Theres no essential difference for our purposes.
Examples:

Notes: Note that the last example is a rearrangement!

Mechanism: Protonation of the alkene by acid (Step 1, arrows A and B)
leads to the more substituted (i.e. stable) carbocation, which is then attacked
by water (Step 2, arrow C). Deprotonation of the oxygen then gives the
neutral alcohol (Step 3, arrows D and E). Note that the acid is regenerated in
step 3, so it acts as a catalyst.

Notes: Its probably more reasonable to show water as the base in step 3,
but HSO4(-) was used here for simplicitys sake. Note that the acid is
catalytic.
In this example a secondary carbocation is formed: if C-3 were a tertiary or
quaternary carbon, a rearrangement would have occurred.
Chlorination (Cl2)
Description: Treatment of alkenes with chlorine (Cl2) leads to formation of
vicinal dichlorides (1,2-dichlorides)

Notes: Note that the chlorines add to opposite faces of the double bond
(anti-addition)
Examples:

Notes: Again note that the stereochemistry is trans.

Mechanism: Attack of the alkene on chlorine (Step 1, arrows A and B) gives
the chloronium ion, which is then attacked by chloride at carbon to give the
1,2-dichloride (vicinal dichloride). Note that this should occur at the more

substituted carbon of the chloronium ion where appropriate (Markovnikoff

addition).

Notes: Note that only one enantiomer is shown here: chlorine has an equal
chance of adding to either face of the alkene, and thus a 1:1 mixture of
enantiomers will be formed.
Bromination (Br2)

Description: Treatment of alkenes with bromine (Br2) gives vicinal

dibromides (1,2-dibromides).
Notes: The bromines add to opposite faces of the double bond (anti
addition). Sometimes the solvent is mentioned in this reaction a common
solvent is carbon tetrachloride (CCl4). CCl4 actually has no effect on the
reaction, its just to distinguish this from the reaction where the solvent is
H2O, in which case a bromohydrin is formed (see also).

Notes: Again note that in the first example CCl4 is merely the solvent and in
these cases has no effect on the reaction (unlike when water or alcohols are
the solvent see bromohydrin formation page).
Mechanism:
Attack of the alkene on bromine (Step 1, arrows A and B) gives the
bromonium ion, which is attacked at the backside by bromide ion to give
the trans-dibromo product. Note that the bromines are delivered to opposite
sides of the alkene (anti addition).

Notes: Note that a 1:1 mixture of enantiomers will be formed in this

reaction. The enantiomer formed will depend on which face of the alkene the
bromine adds to.
Iodination (I2)
Description: Treatment of alkenes with iodine (I2) leads to the formation of
vicinal diiodides (1,2-diiodides).

Notes: The iodides add to opposite faces of the double bond (anti
addition)
Examples:

Notes: Note that the stereochemistry is trans in these products.

Mechanism: Attack of the alkene on iodine gives the iodonium ion (Step 1,
arrows A and B). The iodonium ion is then attacked by iodide ion at the most
substituted carbon where applicable (Markovnikoff) to give the 1,2-diiodide.

Chlorohydrin Formation (Cl2/H2O)

Description: Alkenes treated with chlorine (Cl2) in the presence of water
will form chlorohydrins. The stereochemistry of the products is anti.

Notes: Note that this reaction is Markovnikoff selective (OH ends up on most
substituted carbon of the alkene) and the OH and Cl groups have opposite
stereochemistry [where possible]
Examples:

Notes:Note how in examples 1 and 2 the oxygen is attached to the most

substituted carbon (Markovnikoff). Note the trans stereochemistry in
example 1. Note that the third example this is an example of an
intramolecular reaction.
Mechanism: The alkene attacks Cl2 to form a chloronium ion (Step 1,
arrows A and B) which is attacked on the more substituted carbon by water
(Step 2, arrows C and D). The positively charged oxygen is then
deprotonated to give the neutral alcohol.

Notes: Note that its actually more reasonable to show water acting as the
base in step 3 (its a stronger base). Also, although not shown here the
oxygen and chlorine should be trans to each other since the bromonium ion
undergoes backside attack by the water.
Bromohydrin formation (Br2/H2O)
Description: Alkenes treated with bromine (Br2) in the presence of water
will form bromohydrins.

Notes: Note that this reaction is Markovnikoff selective and delivers

the trans-product. This is essentially the same reaction as with NBS.
Examples:

Notes: Note how in examples 1 and 2 the oxygen is attached to the most
substituted carbon (Markovnikoff). The trans-stereochemistry is evident in
example 1. Finally in the third example this is an example of an
intramolecular reaction often gives students trouble!
Mechanism: The alkene attacks Br2 to form a bromonium ion (Step 1,
arrows A and B) which is then attacked on the more substituted carbon by
water (Step 2, arrows C and D). The positively charged oxygen is then
deprotonated to give the neutral alcohol.
Acid-Catalyzed Addition of Alcohols
Description: Alkenes treated with acid in the presence of an alcohol (usually
as solvent) form ethers.

Notes: The acid used typically has a poorly nucleophilic counter-ion, like
H2SO4 or p-TsOH. Often, H+ is just written as the acid. [If an acid with a

relatively nucleophilic counter ion like HCl were written, then there might be
some competition with Cl- adding to the carbocation that is formed].
The alcohol is generally used as solvent. Note that the addition is
Markovnikov (H adds to least substituted carbon of the alkene, oxygen
adds to most substituted carbon).
Examples:

Notes: Note that the addition is always Markovnikov; the proton adds to the
least substituted carbon of the alkene, and the alcohol adds to the most
substituted carbon. Example 1 shows H+ as acid; note how there is
essentially no difference in changing to H2SO4 or p-TsOH.
The reaction proceeds through a carbocation intermediate, so
rearrangements can occur (example 4).
Intramolecular reactions are possible (example 5).
Mechanism: This reaction proceeds similarly to other Markovnikov
additions to alkenes such as addition of hydrogen halides. In the first step
the alkene is protonated by acid so as to produce the most stable
carbocation (Step 1, arrows A and B). The carbocation then formed is
attacked by the alcohol (Step 2, arrow C) leading to formation of the C-O
bond. In the final step, the positively charged oxygen is deprotonated to give
the neutral ether.

Notes: Note that although here -OSO3H is shown as doing the final
deprotonation, it is just as correct (if not more correct) to show the alcohol
solvent performing this deprotonation.

Notes: Its probably more reasonable to show water as the base in step 3.
Although not important for this molecule, the bromine and oxygen are in
atrans orientation since water attacks the bromonium ion from the back.
Oxymercuration ( Hg(OAc)2 / H2O )
Description: Alkenes treated with mercuric acetate [ Hg(OAc)2 ] and water
will be hydrated to form alcohols, after addition of NaBH4.

Notes: This reaction follows Markovnikovs rule the oxygen adds to the
more substituted carbon. The purpose of the second step (NaBH4) is to
remove the mercury.
Examples:

Notes: See that the oxygen is attached to the more substituted carbon of
the alkene. Also, there is no clear preference for syn or anti addition. In the
third example notice that here Markovnikoffs rule gives us no clear
preference for which carbon to add the oxygen to, so we obtain a mixture.
Mechanism: The alkene adds to Hg(OAc)2, displacing acetate and forming a
mercuronium ion (Step 1, arrow A and B). Next, the more substituted carbon
is attacked by water (Step 2, arrows C and D). The resulting protonated
alcohol is then deprotonated by acetate (Step 3, arrows E and F). Removal of

mercury is done with NaBH4. The mechanism of this step is generally not
considered to be important for Org 1 / Org 2. However it is shown separately
below.

Note that attack of alcohol (Step 2) occurs trans to the mercury, although
that is not depicted here. Removal of mercury leads to the formation of a
free radical (Step 6) so the reaction is not stereoselective.
Heres the mechanism of the reduction.

Oxymercuration ( Hg(OAc)2 / ROH )

Description: When an alkene is treated with an alcohol in the presence of
mercuric acetate [Hg(OAc)2] it will add to the more substituted position of the
alkene (Markovnikoff) to give an ether. The mercury can then be removed
using NaBH4.

Notes: The alcohol is generally used as the solvent here.

Examples:

Notes: Note that in the second reaction, no rearrangement occurs (this

would have happened for the acid-catalyzed reaction).
The last example is an intramolecular reaction often gives students a hard
time.
The byproducts in all cases are NaOAc, HOAc, BH3 and Hg(s)
Mechanism: The alkene attacks Hg(OAc)2, displacing acetate and forming a
mercuronium ion (Step 1, arrows A and B). Next, the more substituted carbon
is attacked by the solvent alcohol (Step 2, arrows C and D). The resulting
protonated ether is then deprotonated by acetate (Step 3, arrows E and F).
Removal of mercury is done with NaBH4. The mechanism of this step is not
generally considered to be important for Org 1/ Org 2. However, it is shown
separately below.

Mechanism for removal of mercury:

Notes: Attack of alcohol (Step 2) occurs trans to the mercury, although that
is not depicted here. Removal of mercury proceeds through formation of a
free radical, so the reaction is not stereoselective.
Hydroboration-Oxidation (BH3 / H2O2)
Description: Hydroboration-oxidation transforms alkenes into alcohols. It
performs the net addition of water across an alkene.

Notes: Note that the oxygen is always attached at the less substituted
carbon (anti-Markovnikoff). Furthermore the stereochemistry is always syn (H
and OH add to same side of the alkene).
The boron byproduct will depend on the # of equivalents of BH3 used reative
to the alkene. Here their molar ratio is 1:1. One equivalent of BH3 can
hydroborate up to 3 equivalents of alkene. BH3-THF is the same as BH3.
Tetrahydrofuran (THF) is merely a solvent. Sometimes B2H6 is written, which
is another form of BH3. It behaves in exactly the same way as BH3.
You might also see 9-BBN or (Sia)2BH. These are hydroboration reagents in
which two of the H atoms in BH3 have been replaced by carbon atoms. They
will do the exact same reaction as BH3.
Examples:

Notes: Note in example 2 that the hydrogen and oxygen add to the same
side of the alkene (syn addition)
Mechanism:
The reaction begins with the concerted syn addition of B and H across the
double bond, with the boron adding to the less substituted carbon (Step 1,
arrows A and B). In the second step, hydrogen peroxide and a base such as
NaOH are added. the NaOH deprotonates the hydrogen peroxide (Step 2,
arrows C and D) which makes the conjugate base of hydrogen peroxide (a
better nucleophile than H2O2 itself). The resulting NaOOH then attacks the
boron (Step 3, arrow E). This sets up the key migration step, where the
carbon-boron bond migrates to the oxygen bound to boron, breaking the
weak oxygen-oxygen bond (Step 4, arrows F and G). The OH expelled then
comes back to form a bond on the boron (Step 5, arrows H and I) resulting in
the deprotonated alcohol (alkoxide). The alkoxide is then protonated by
water or some other comparably acidic species (Step 6, arrows J and K).

Notes: In step 1 the addition is syn and the reaction is concerted. If excess
alkene is present the two remaining B-H bonds can do subsequent
hydroborations. Note that only one enantiomer is shown here (but the
product will be racemic) The migration step (Step 4, arrows F and G) occurs
with retention of stereochemistry at the carbon.
For the last step its reasonable to use water, HOOH or any other comparably
acidic species as the acid.
Epoxides from alkenes (RCO3H e.g. mCPBA)
Description: meta-chloroperoxybenzoic acid (m-CPBA) or other peroxyacids
such as peracetic acids will convert alkenes into epoxides.

Notes: The stereochemistry of this reaction is always syn (both bonds to

oxygen are formed on the same side of the alkene).
Examples:

Notes: Note that example 2 just shows m-CPBA written out its in no way
different from the others. Examples 3 and 4 show that the reaction
isstereospecific that is, trans alkenes give trans products, and cis alkenes
give cis products. Also note there is no reaction with alkynes.
Mechanism:

This is a reaction which the arrow pushing formalism isnt very good at
describing. Instead, a transition state is shown here, which shows breaking of
the CC bond at the same time the CO bonds are forming. At the same
time the OO bond is breaking and the hydrogen from the OH is being picked
up by the carbonyl oxygen.
Notes: Note that the byproduct here is m-chlorobenzoic acid (in grey).
Dihydroxylation (OsO4)

Description: Treatment of alkenes with osmium tetroxide (OsO4) leads to

the formation of 1,2-diols (vicinal diols).

Notes: The reaction proceeds with syn stereochemistry on the alkene,

meaning that the two alcohols end up on the same side of the alkene.
Sometimes a reducing agent like NaHSO3 or KHSO3 is added to remove the
osmium at the end. Regardless, the key reaction is the same.
Also note that cold, alkaline KMnO4 does exactly the same reaction.
Examples:

Notes: The reaction is essentially the same regardless of whether KHSO3 is

present. Also note that the reaction does not occur with alkynes.
Mechanism: Osmium tetroxide adds to one face of the alkene through a
cycloaddition reaction (Step 1, arrows A, B, and C) to give a cyclic osmium
compound (osmate ester). The osmate ester is then reduced with NaHSO3
or KHSO3 and hydrolyzed to the diol through a very long process that is, to
be frank, excruciatingly tedious to write out and not generally bothered with
in Org 1 and Org 2.

Notes: There is also a variation where OsO4 is used in catalytic amounts and
a stoichiometric oxidant such as N-methylmorpholine N-oxide (NMO) is used
to regenerate OsO4.
Dihydroxylation of alkenes (KMnO4)
Description: Treatment of alkenes with cold, dilute basic KMnO4 leads to
1,2-diols (vicinal diols).

Notes:
The reaction proceeds with syn stereochemistry of the alkene,
meaning that the two alcohols end up on the same side of the alkene
Also note that osmium tetroxide (OsO4) does exactly the same
reaction.
Examples:

Notes: The reaction works well so long as it is kept cold. If higher

temperatures are used, cleavage of the diol to give carbonyl compounds is
observed. Note that the reaction does not occur with alkynes.
Mechanisms: Potassium permanganage adds to one face of the alkene
through a cycloaddition reaction (Step 1, arrows A, B and C) to give a cyclic
manganese compound (manganate ester). The manganate ester is then
reduced with NaHSO3 or KHSO3 and hydrolyzed to the diol through a very
long process that is excruciatingly boring to write out and generally not
bothered with in Org 1/ Org 2

Notes: The boring part goes something like this: water attacks Mn, transfer
proton to O, break MnO bond, then add second equivalent of water to Mn,
transfer proton to O, break MnO bond. This gives the free diol.
Cyclopropanation (CH2N2 or CH2I2/Zn-Cu)

Description: Alkenes treated with methylene carbene (:CH2) will form

cyclopropanes.

Notes: In practice there are several ways to write this. Two common
examples are with diazomethane (CH2N2) in the presence of heat () or light
(h), with diiodomethane (CH2I2) in the presence of zinc-copper couple (ZnCu). For our purposes the end result is exactly the same. The example with
CH2I2 and Zn-Cu is called the Simmons-Smith reaction.
Examples:

Notes: Note that the syn product is always formed. See how the hydrogens
on the double bond have become dashes?
Mechanism: Treatment of diazomethane with light (or heat) results in
fragmentation of the CN2 bond (Step 1, arrow A), liberating nitrogen gas.
The resulting carbene then does the cyclopropanation of the alkene (Step 2,
arrows B and C). Note that the reaction proceeds through a concerted
transition state, so B and C happen simultaneously.

For the reaction with ZnCu the mechanism is essentially the same with a
slight twist. First, Zn inserts itself into the CI bond in a mechanism similar to
that for Grignard formation but is not depicted here (Step 1). Then, breakage

of the CZn bond (Step 2, arrow A) leads to a species that performs the
cyclopropanation (Step 3, arrows B and C) to give the cyclopropane. It also
proceeds through a concerted transition state.

Notes: This example with ZnCu is called the Simmons Simith

cyclopropanation
Dichlorocyclopropanation
Description: Treatment of chloroform (CHCl3) with strong base (NaOH) leads
to the formation of a dichlorocarbene, which then can form a cyclopropane
when added to an alkene.

Notes: The byproducts of this reaction are NaCl and H2O

Examples:

Notes:
Mechanism: Deprotonation of chloroform (Step 1, arrows A and B) leads to
formation of a short-lived anion. Loss of chloride ion from this ion (Step 2,
arrow C) leads to formation of a carbene. When combined with an alkene, a
cyclopropane will form (Step 3, arrows D and E).

Notes: This reaction proceeds through a concerted transition state (see

bottom left).
Ozonolysis of alkenes (reductive workup)
Description: Ozone will cleave carbon-carbon double bonds to give
carbonyl compounds such as aldehydes or ketones, after treatment with a
reducing agent such as zinc or dimethyl sulfide (reductive workup)

Notes: Acid here could be written as H3O+ , H+, acid, etc. Its not
crucial.
Examples:

Notes: Note that any alkene carbon that has a CH bond is converted into
an aldehyde. Any alkene carbon with two CC bonds is converted into a
ketone. Example 3 is the cleavage of a cyclic alkene to give a linear
compound. In example 4, reduction with Me2S (DMS) is in no way different
from reduction with Zn.
Mechanism: The first step of the reaction is a cycloaddition of ozone with
the alkene (Step 1, arrows A, B, and C). The second step is
areverse cycloaddition, resulting in cleavage of the carbon-carbon single
bond (Step 2, arrows D, E and F). The oxygen of the carbonyl oxide then
performs a 1,2-addition on the other carbonyl (Step 3, arrows G and H) giving
a negatively charged oxygen that performs a 1,2-addition on the carbonyl
carbon of the carbonyl oxide to give the ozonide. (Step 4, arrows I and J).

For reductive workup the mechanism is generally not considered so

important for the purposes of Org 1/ Org 2, but here it is! In the reduction
step, zinc attacks one of the oxygens of the ozonide, breaking the weak OO
bond (Step 5, arrows K and L). The resulting anion then performs a 1,2elimination (Step 6, arrows M and N) to give one of the fragments, followed
by a second 1,2-elimination (Step 7, arrows O and P).

Ozonolysis (O3) Oxidative Workup

Description: Ozone will cleave carbon-carbon double bonds to give
ketones/carboxylic acids after oxidative workup.

Notes: The initial product of this reaction is an ozonide. Treatment of the

ozonide with acid and an oxidant such as hydrogen peroxide (H2O2) will
convert any aldehydes to carboxylic acids. Note that any CH bonds on the
alkenes are converted to COH bonds, giving carboxylic acids.
Examples:

Notes: Note how every CH bond on the alkene is converted into a COH
bond to give a carboxylic acid. Also note that example 3 shows cleavage of a
cyclic alkene to give a linear compound. In example 4, cleavage of a terminal
alkene results in CO2.
Mechanism: The first step of the reaction is a cycloaddition of ozone with
the alkene (Step 1, arrows A, B, and C). The second step is a reverse
cycloaddition, resulting in cleavage of the carbon-carbon single bond (Step 2,
arrows D, E, and F). The oxygen of the carbonyl oxide then performs a 1,2addition on the other carbonyl (Step 3, arrows G and H) giving a negatively
charged oxygen that performs a 1,2-addition on the carbonyl carbon of the
carbonyl oxide to give the ozonide (Step 4, arrows I and J).

With warming, the ozonide breaks down to the aldehyde and a carbonyl
oxide (Step 5, arrows K, L, and M). Addition of peroxide to the aldehyde then
occurs (Step 6, arrows N and O). This is followed by proton transfer (Step 7,
arrows P and Q) and then removal of a proton with base to give the carbonyl
(C=O) (Step 8, arrows R, S, and T).

Notes: There are other reasonable ways to draw this mechanism,

particularly other ways of drawing proton transfer in Step 7 and other
species that could act as bases in Step 8.
Oxidative Cleavage of Alkynes with KMnO4
Description: Potassium permanganate (KMnO4) will cleave alkynes to give
carboxylic acids.

Notes: The same reaction can be performed with ozone (O3)

Examples:

Notes: Note where a terminal alkyne is being cleaved (examples 2 and 4)

one of the products is carbon dioxide.
Mechanism: For the purposes of Org 1 / Org 2 the mechanism of this
reaction is not considered important. However the first step is almost
certainly the cycloaddition of MnO4 to the triple bond, followed by oxidative
cleavage.
Hydrogenation of Alkenes to give Alkanes
Description: In the presence of a metal catalyst such as palladium,
hydrogen will add to alkenes to give alkanes.

Notes: Many other metal catalysts can be used, such as platinum (Pt), nickel
(Ni), or Rh (rhodium)
Examples:

Notes: Note that the stereochemistry of addition to the alkene is syn (see
the second example). Furthermore note that deuterium (the heavy isotope of
hydrogen) can also be used instead of hydrogen. It works exactly the same
way!
Mechanism: For the purposes of Org 1/ Org 2 the exact mechanism of this
reaction is generally not considered important. However it does follow the
following sequence: hydrogen and the alkene are both adsorbed onto the
surface of the metal, and the hydrogen-hydrogen bond is broken. Then, both
hydrogen atoms are delivered syn to the alkene.

Additions to alkenes with 1,2-hydride shifts

Description: When secondary (or primary) carbocations are formed,
adjacent to a more substituted carbon, hydrogen atoms can shift. This leads
to formation of a more stable carbocation.

Notes: Note how the blue hydrogen has shifted positions and the X [which
could be Br, Cl, I, or OH] is attached to where the H used to be.
Examples:

Notes: Note that the first two examples show rearrangement to give mroe
stable tertiary carbocations, whereas the last example shows a
rearrangement to give a resonance stabilized benzylic carbocation.
Mechanism: The first step of the reaction is formation of a carbocation.
Here, the formation of a carbocation from addition of HBr to an alkene is
shown (Step 1, arrows A and B). Since we have a secondary carbocation
adjacent to a tertiary carbon, shift of a hydrogen to the secondary
carbocation will results in a (more stable) tertiary carbocation (Step 2, arrow
C). The tertiary carbocation is then trapped, in this case, by Br() (Step 3,
arrows D). The rearrangement step goes through a transition state such as
the one pictured.

Free Radical Bromination of Alkanes

Description: When treated with bromine (Br2) and light (h) alkanes are
converted into alkyl bromides. In the absence of any double bonds, with
Br2this is selective for tertiary carbons.

Notes: Light (h) is the initiator for this reaction.

Examples:

Notes: Note that each of these reactions produces HBr as a byproduct. If

this reaction occurs at a stereocenter, a mixture of alkyl bromides will be
obtained.
This table allows for the relative comparison of the selectivity of radical
chlorination and bromination (reaction rates with typical primary, secondary,
tertiary alkyl C-H bonds)

Mechanism: When treated with light, Br2 fragments to bromine radicals

(Step 1, arrow A). At any given time only a small amount of these radicals is
present. Theres lots of leftover Br2! Remember this as it comes up in step 3.
Bromine radical then abstracts a hydrogen from the tertiary carbon, leaving
behind the tertiary radical (Step 2, arrows B and C). The tertiary radical then
reacts with Br2, giving the tertiary bromide (Step 3, arrows D and E).

Notes: Avoid the common mistake of having the radical react with Br in
the third step thats not a propagation reaction, thats termination!
Note that tertiary radicals are more stable than secondary or primary
radicals and thus require the least energy to form (another way of saying this
is that tertiary C-H bonds are weaker than secondary and primary C-H
bonds). The higher selectivity of this reaction for tertiary C-H (when
compared with chlorination) is a reflection of the fact that formation of the
weaker HBr bond provides less of a driving force for this reaction as
compared to HCl (which is a stronger bond).
Free Radical Addition of HBr To Alkenes
BY JAMES LEAVE A COMMENT

Description: Treatment of an alkene with HBr in the presence of catalytic

amounts of a radical initiator (such as peroxides) in addition to heat or light
leads to addition of HBr to the alkene in anti-Markovnikov fashion (note that
the Br adds to the less substituted side of the alkene and the H adds to the
more substituted side).
Notes: A common initiator for this purpose is t-butyl peroxide (t-BuO-Ot-Bu)
but in general the peroxide will be written, RO-OR. Heat or light is required
to break the weak OO bond. Again, note that this reaction is in contrast to

normal addition of HBr which proceeds in Markovnikov fashion.

Again, the initiator is generally catalytic (less than 1 equiv required)
Examples:

Notes: Note that either light (h) or heat ( ) can be used to initiate the
reaction, and the initiator can be written variably as peroxides, RO-OR or
even given specifically, as in the case of t-butyl peroxide in the bottom
example. The reaction is not stereospecific, so if new stereocenter(s) are
formed, such as in the bottom example, a mixture of stereoisomers may be
obtained.
Note also that Br adds to the less substituted carbon of the alkene.
Mechanism: The purpose of heat/light is to cause homolytic fragmentation
of the weak OO bond of the peroxide catalyst (Step 1 arrow A) . This leads
to reversible formation of alkoxy radicals, which can then remove a hydrogen
(homolytically) from HBr to give the alcohol (R-OH) and bromine radical Br
(Step 2, arrows B and C) . The purpose of the peroxide is just to get the free
radical chain reaction going (that is why only a catalytic amount is
necessary). However, at least 1 equiv of H-Br is necessary to convert all the
alkene to the addition product.

Once the bromine radical is formed, it can then add to the alkene. Note that
since radical stability increases with increasing substitution (i.e. primary <
secondary << tertiary) addition will occur such as to form the most
substituted (i.e. most stable) radical which means that Br will add to
the least substituted carbon of the alkene (step 3, arrows D and E). In
this case a secondary radical is formed, which then reacts with HBr to form
the alkyl halide product and to regenerate bromine radical (Step 4, arrows F

and G).

Althou
gh often not shown, termination occurs when the concentration of alkene
or H-Br becomes low. Termination is the combination of two radicals to form a
new bond. One possible termination step might be the combination of the
alkyl radical with bromine radical, shown below:

Notes: This radical addition process only works for H-Br, not H-Cl or H-I.
Since free-radicals can participate in reactions from either face, if a
stereocenter is formed, a mixture of stereoisomers will be obtained. For
example, in the alkene below, the first addition (of Br) can occur from either
face, as can the attack of the radical on H-Br. Four stereoisomers are

obtained.

Sharpless Epoxidation
BY JAMES LEAVE A COMMENT
Description: The Sharpless Epoxidation is an enantioselective epoxidation
of allylic alcohols.

Notes: The Sharpless epoxidation only works for alkenes adjacent to an

alcohol (CH2OH). The oxidant is t-butyl hydroperoxide, sometimes written
(CH3)3COOH or abbreviated TBHP. The catalyst is titanium tetraisopropoxide,
written Ti[Oi-Pr]4 or Ti[OCH(CH3)2]4. The additive that imparts chirality is
diethyl tartrate (DET). Choosing (+) or () diethyl tartrate [full names: L-(+)diethyl tartrate and D()-diethyl tartrate one can omit the L or D without
penalty] allows one to choose the major enantiomer that is formed in this
reaction [see Mechanism section for specifics].
The major product can be predicted by use of a mnemonic (see below).
Examples:

Notes: As far as the reagents are concerned, each of these examples just
shows different ways of representing the key titanium catalyst and t-butyl
hydroperoxide. The only difference is in the choice of diethyl tartrate
(sometimes abbreviated DET) enantiomer.
Example 1 shows an epoxidation of an alkene drawn in the side view which
clearly shows that using ()-diethyl tartrate leads to epoxidation from the top
face when the allylic alcohol is drawn in this orientation.
Example 2 shows that epoxidation only occurs on the alkene adjacent to
CH2OH, the other alkene is untouched [BTW, this is because the OH
coordinates to titanium]
Examples 3 and 4 show the major products formed with each of these
alkenes, predicted by using the mnemonic (below).
Example 5 shows that no reaction occurs when an alkene without a
neighbouring alcohol is used.
Mechanism: Without going into specific details, what happens in the
Sharpless epoxidation is that the titanium binds to the allylic alcohol, tbutylhydroperoxide, and the tartate in such a way as to provide a chiral
environment whereby one face of the alkene is preferentially exposed to the
oxidant. The outcome of a Sharpless epoxidation can be predicted by using

the following mnemonic. Placing the CH2OH group in the upper right hand
quadrant, using ()-DET will lead to epoxidation of the top face, whereas (+)DET will lead to epoxidation of the bottom face.