"Master Organic Chemistry"

Summary Sheet - Additions to Alkenes

masterorganicchemistry.wordpress.com
June 2010. Version 1.0
If you understand just these 5 things, you'll be alright.
It's easy to get bogged down in details. Not all the details are
equally important. Here are 5 key things to understand.
1. Understand the order of carbocation stability. Tertiary
carbocations are most stable, followed by secondary and primary.
Understand why.
2. The most negative group will bond to the carbon best able to
support positive charge. This follows for the acid additions (e.g. HCl,
HBr) AS WELL AS hydroboration, since H carries the negative charge in
the HB bond (due to the low electronegativity of B).
3. Acids + alkenes = free carbocations. With free carbocations,
there can be no stereoselectivity (i.e. they are stereorandom) Also, be
alert for the possibility of rearrangements, especially where tertiary
carbocations can be formed.
4. Halides + alkenes = bridging cations. These will provide
anti products. These cations never rearrange.
5. If there's a metal involved, it's probably syn. The only exception
is oxymercuration.

R
R

R
H

R
R

R
H

R
R

R
H

R
R

R
H

R
R

R
H

1) BH3
2) NaOH,
H2O2
1) Hg(OAc)2
H2O

HO

2) NaBH4

H2SO4
H2O

R
H

R H

R H

R H

R
H

Cl2

R
R

R
H

OsO4

R
R

R
H

R
R

R
H

Note - this sheet is not meant to be comprehensive. Your course

may provide additional material, or may not cover some of the
reactions shown here. Your course instructor is the final authority.

R
R

R
H

cold, dilute

R
R

R
H

peroxides

stereorandom
HCl and HBr (as well as HI, not pictured) protonate the alkene to give a free
carbocation which can then be trapped by the halide anion. Stereorandom

Markovnikoff

stereorandom

N/A

anti addition

R
H

R
R

Br

R
H

Bromonium ion mechanism

Br or H2O/ROH depending on solvent

R
H

Markovnikoff

anti addition

R
H

N/A

anti addition

As with bromination, above. Although not depicted, use of water or alcohol as solvent
will also lead to formation of the halohydrin product (also anti).

HO OH
R
R
R
H

N/A

syn addition

OH

Cl

R
R

R
H

H2

R
R

Pt

KMnO4

H H

S
O3

H2O2

R
H

N/A

syn addition

R
H

N/A

syn addition

N/A

syn addition

HO OH
R
R
R
H

HBr

CH3

R
R

O3

This sheet copyright 2010, James A. Ashenhurst

masterorganicchemistry.wordpress.com

Markovnikoff

Strong acid protonates the alkene, generating free carbocation. Watch out for
possibility of rearrangements when a tertiary carbocation could be generated through a 1,2 shift.
HSO4 anion is not strongly nucleophilic, hence it does not add. Stereorandom because
of the free carbocation.

Osmium is a transition metal. The tools won't be given in this course to fully understand how this reaction
works. Occasionally a second reagent like NaHSO3, H2S, or Na2S2O3 is also given as a reactant in this
reaction - minor detail, it's used to remove the osmium from the hydroxyl groups.

Omissions, Mistakes, Suggestions?

james@writechem.com

stereorandom

Br

Study Questions:
1. What are some examples of Markovnikoff-selective reactions?
2. Why are these reactions selective for the Markovnikoff products?
3. What are some examples of anti-Markovnikoff selective reactions?
4. Why are they selectve for the anti-Markovnikoff products?
5. What are some examples of anti-selective reactions. Why do they
give the anti-products?
6. What are some examples of syn-selective reactions?
7. Write down combinations of alkene and reagent that would
provide you with:
i) a primary alcohol
ii) a secondary alcohol
iii) a tertiary alcohol
iv) an ether

Markovnikoff

Can use an alcohol in place of water. Goes through 3-membered "mercuronium" ion. NaBH4 step removes the
mercury. While the addition is anti, the overall reaction is stereorandom because this step involves a carbon
based free radical (usually not discussed).

The key detail in these reactions is solvent: water and alcohol solvents will form the
halohydrin products (the ones containing the OH and Br). All other solvents (you might
see CCl4, CHCl3, hexane, etc. ) provide the dibromide.

Cl
R
R

R
R

stereorandom

Br

HO
R
R

Br2

Markovnikoff

Br
R
R

H2O

Sometimes you see BH3THF or B2H6 - it's the same reagent in a slightly different form.
The base (can be NaOH, KOH, identity unimportant) helps make H2O2 more reactive. The reaction is anti Markovnikoff because the HB bond is polarized toward H (electronegativity of H = 2.2, B = 2.0) - the H
adds to the carbon best able to stabilize positive charge (i.e. the most substituted one).

Br

HBr

syn addition

Cl

HCl

Br2
R
R

R H

Anti-Markovnikoff

HO

(Sixth thing - less applicable, but still important)

6. If radicals are involved in the mechanism there can be no
stereoselectivity. The two examples are oxymercuration (where NaBH4
converts the CHg bond to CH through a radical process) and the peroxide
induced free radical addition.

H OH
R
H

R
R

Br
anti-Markovnikoff

R H
R
R

R
H

CH3
R
R

R
OH

stereorandom

RCO3H is a per-acid. A common peracid for this reaction is m-CPBA

Cl
(m-chloroperbenzoic acid). If H3O+, heat is written afterwards, this
is opening of the epoxide to give the diol (anti-selective)

O
OH
O
MCPBA

The catalyst can vary - you might see Pd/C or Ni as well. All provide the same product with the same
stereochemistry.

Keywords are "cold, dilute". If "heat" is mentioned in the conditions, the diol will be cleaved to
provide carbonyl compounds (same reaction as ozonolysis with oxidative workup, below.

Peroxides generate the Br radical, which adds to the double bond in the way that will generate the
most stable radical (i.e. the radical will go on to the most substituted carbon). This explains the
selectivity for the anti-Markovnikoff product. It's stereorandom because it goes through a free radical
process.

CH3SCH3 (dimethyl sulfide) is a reducing agent, it will be oxidized to dimethyl sulfoxide.

Hydrogen peroxide is used to obtain the carboxylic acid instead of the aldehyde.