Markovnikovs rule

2 Anti-Markovnikov reactions
Mechanisms that avoid the carbocation intermediate may
react through other mechanisms that are regioselective,
against what Markovnikovs rule predicts, such as free
radical addition. Such reactions are said to be antiMarkovnikov, since the halogen adds to the less substituted carbon, exactly the opposite of Markovnikov reaction. Again, like the positive charge, the radical is most
stable when in the more substituted position. The antiMarkovnikov rule can be best explained by taking an example of addition of hydrogen bromide to propene in
the presence of benzoyl peroxide. The reaction of HBr
with substituted alkenes was instrumental in the study of
free-radical additions. Early chemists discovered that the
reason for the variability of the ratio of Markovnikov to
anti-Markovnikov reaction products was due to the unrealized presence of free radical generating substances such
as peroxides. The explanation is that HBr produces a Br
radical, which then reacts with the double bond. Since
the bromine atom is very large, it is more probable that it
will encounter and react with the least substituted carbon,
in this case the terminal carbon, to produce a primary addition product instead of a, in the case of propene, secondary addition product.

Markovnikovs rule is illustrated by the reaction of propene with

hydrobromic acid

In organic chemistry, Markovnikovs rule or Markownikos rule describes the outcome of some addition reactions. The rule was formulated by Russian chemist
Vladimir Vasilevich Markovnikov in 1870.[1][2]

Explanation

The rule states that with the addition of a protic acid

HX to an unsymmetrical alkene, the acid hydrogen
(H) becomes attached to the carbon with fewer alkyl
substituents, and the halide (X) group becomes attached
to the carbon with more alkyl substituents. Alternatively,
the rule can be stated that the hydrogen atom is added to
the carbon with the greater number of hydrogen atoms
while the X component is added to the carbon with the
fewer number of hydrogen atoms.[3]

A new method of anti-Markovnikov addition has been

described by Hamilton and Nicewicz, who utilize organic
molecules and light from a low-energy diode to turn the
alkene into a cation radical.[4] [5]

The same is true when an alkene reacts with water in an

addition reaction to form an alcohol which involve formation of carbocations. The hydroxyl group (OH) bonds
to the carbon that has the greater number of carbon
carbon bonds, while the hydrogen bonds to the carbon on
the other end of the double bond, that has more carbon
hydrogen bonds.

Anti-Markovnikov behaviour extends to other chemical reactions than just additions to alkenes. One antiMarkovnikov manifestation is observed in hydration
of phenylacetylene that, gold-catalyzed, gives regular
The chemical basis for Markovnikovs Rule is the formaacetophenone but with a special ruthenium catalyst[6] the
tion of the most stable carbocation during the addition
other regioisomer 2-phenylacetaldehyde:[7]
process. The addition of the hydrogen ion to one carbon
atom in the alkene creates a positive charge on the other
carbon, forming a carbocation intermediate. The more
substituted the carbocation (the more bonds it has to carbon or to electron-donating substituents) the more stable
it is, due to induction and hyperconjugation. The major
product of the addition reaction will be the one formed
from the more stable intermediate. Therefore, the major
product of the addition of HX (where X is some atom
more electronegative than H) to an alkene has the hydrogen atom in the less substituted position and X in the more
substituted position. However, the other less substituted, Anti-Markovnikov hydration
less stable carbocation will still be formed to some degree, and will proceed to form the minor product with Anti-Markovnikov behavior can also manifest itself in
certain rearrangement reactions. In a titanium(IV)
the opposite attachment of X.
1

chloride-catalyzed formal nucleophilic substitution at

enantiopure 1 in the scheme below, two products are
formed 2a and 2b. Due to the two chiral centers in
the target molecule, the carbon carrying chlorine and the
carbon carrying the methyl and acetoxyethyl group, four
dierent compounds are to be formed: 1R,2R- (drawn as
2b) 1R,2S- 1S,2R- (drawn as 2a) and 1S,2S- . Therefore
both of the depicted structures will exist in a D- and an
L-form. :[8]

Letters 8 (25): 58536. doi:10.1021/ol062455k. PMID

17134289.
[8] Nishizawa, Mugio; Asai, Yumiko; Imagawa, Hiroshi (2006). TiCl4Induced Anti-Markovnikov Rearrangement.
Organic Letters 8 (25): 57936.
doi:10.1021/ol062337x. PMID 17134274..

4 See also
Zaitsevs rule

5 External links
Khan academy lecture

Anti-Markovnikov rearrangement

This product distribution can be rationalized by assuming that loss of the hydroxy group in 1 gives the tertiary
carbocation A, which rearranges to the seemingly less attractive secondary carbocation B. Chlorine can approach
this center from two faces leading to the observed mixture
of isomers.
Another notable example of anti-Markovnikov addition
is hydroboration.

References

[1] W. Markowniko (1870). Ueber die Abhngigkeit der

verschiedenen Vertretbarkeit des Radicalwasserstos in
den isomeren Buttersuren. Annalen der Pharmacie 153
(1): 22859. doi:10.1002/jlac.18701530204.
[2] Hughes, Peter (2006).
Was Markovnikovs Rule
an Inspired Guess?". Journal of Chemical Education 83 (8): 1152. Bibcode:2006JChEd..83.1152H.
doi:10.1021/ed083p1152.
[3] Organic Chemistry, 6th Edition, by John McMurry. Section 6.9, page 187
[4] http://cen.acs.org/articles/91/i15/
Light-Driven-Reaction-Modifies-Double.html
[5] http://pubs.acs.org/doi/abs/10.1021/ja309635w?source=
cen
[6] catalyst system based on in-situ reaction of ruthenocene
with Cp and naphthalene ligands and a second bulky
pyridine ligand
[7] Labonne, Aurlie; Kribber, Thomas; Hintermann, Lukas
(2006). Highly Active in Situ Catalysts for AntiMarkovnikov Hydration of Terminal Alkynes. Organic

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