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ChemWiki: The Dynamic Chemistry Hypertext > Organic Chemistry > UMM chemwiki project > Alkenes and alkynes > Reactions of alkenes-an overview > Oxymercuration & Demercuration: A Special Electrophilic Addition

Oxymercuration & Demercuration: A Special Electrophilic Addition

Oxymercuration is a special electrophilic addition. It is anti-stereospecific and regioselective. Regioselectivity is a process in which the substituents choses one direction it prefers to be attached to over all the other possible directions. The good thing about this reaction is that there are no carbocation rearrangement due to stabilization of the reactive intermediate. Similar stabilization is also seen in bromination addition to alkenes.


Carbocation rearrangement is a process in which the carbocation intermediate can form a more stable ion. With carbocation rearrangement, the reaction would not be able to hydrate quickly under mild conditions and be produced in high yields. This reaction is very fast and proceeds with 90% yield.

This reaction involves a mercury acting as a reagent attacking the alkene double bond to form a Mercurinium Ion Bridge. A water molecule will then attack the most substituted carbon to open the mercurium ion bridge, followed by proton transfer to solvent water molecule.

The organomercury intermediate is then reduced by sodium borohydride - the mechanism for this final step is beyond the scope of our discussion here. Notice that overall, the oxymercuration - demercuration mechanism follows Markovnikov's Regioselectivity with the OH group is attached to the most substituted carbon and the H is attach to the least substituted carbon. The reaction is useful, however, because strong acids are not required, and carbocation rearrangements are avoided because no discreet carbocation intermediate forms.


  1. Vollhardt, K. Peter C. Organic chemistry structure and function. New York: W.H. Freeman, 2007.
  2. Smith, Michael B., and Jerry March. March's Advanced Organic Chemistry Reactions, Mechanisms, and Structure (March's Advanced Organic Chemistry). New York: Wiley-Interscience, 2007 2007.
  3. Roderic P. Quirk , Robert E. Lea, Reductive demercuration of hex-5-enyl-1-mercuric bromide by metal hydrides. Rearrangement, isotope effects, and mechanism, J. Am. Chem. Soc., 1976, 98 (19), pp 5973–5978.

Some Practice Problems

What are the end products of these reactants?

Practice Problems (1).bmp


Answers (1).bmp

The end product to these practice problems are pretty much very similar. First, you locate where the double bond is on the reactant side. Then, you look at what substituents are attached to each side of the double bond and add the OH group to the more substituent side and the hydrogen on the less substituent side.


  • Duyen Dao-Tran

Organic Chemistry With a Biological Emphasis by Tim Soderberg (University of Minnesota, Morris)

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