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ChemWiki: The Dynamic Chemistry Hypertext > Organic Chemistry > UMM chemwiki project > Alkenes and alkynes > Oxidation of Alkenes

Oxidation of Alkenes


Hydroxylation of alkenes


Dihydroxylated products (glycols) are obtained by reaction with aqueous potassium permanganate (pH > 8) or osmium tetroxide in pyridine solution. Both reactions appear to proceed by the same mechanism (shown below); the metallocyclic intermediate may be isolated in the osmium reaction. In basic solution the purple permanganate anion is reduced to the green manganate ion, providing a nice color test for the double bond functional group. From the mechanism shown here we would expect syn-stereoselectivity in the bonding to oxygen, and regioselectivity is not an issue.


When viewed in context with the previously discussed addition reactions, the hydroxylation reaction might seem implausible. Permanganate and osmium tetroxide have similar configurations, in which the metal atom occupies the center of a tetrahedral grouping of negatively charged oxygen atoms. How, then, would such a species interact with the nucleophilic pi-electrons of a double bond? A possible explanation is that an empty d-orbital of the electrophilic metal atom extends well beyond the surrounding oxygen atoms and initiates electron transfer from the double bond to the metal, in much the same fashion noted above for platinum. Back-bonding of the nucleophilic oxygens to the antibonding π*-orbital completes this interaction. The result is formation of a metallocyclic intermediate, as shown above.



Epoxidation of alkenes


Some oxidation reactions of alkenes give cyclic ethers in which both carbons of a double bond become bonded to the same oxygen atom. These products are called epoxides or oxiranes. An important method for preparing epoxides is by reaction with peroxyacids, RCO3H. The oxygen-oxygen bond of such peroxide derivatives is not only weak (about 35 kcal/mole), but in this case is polarized so that the acyloxy group is negative and the hydroxyl group is positive (recall that the acidity of water is about ten powers of ten weaker than that of a carboxylic acid).



The epoxidation reaction is believed to occur in a single step with a transition state incorporating all of the bonding events shown in the equation. Consequently, epoxidations by peroxyacids always have syn-stereoselectivity, and seldom give structural rearrangement.


Epoxidation of alkenes is also an important biochemical reaction.  For example, epoxidation of an alkene group in a precursor molecule called squalene is a key step in the pathway by which our bodies synthesize cholesterol.


squalene epoxidase.png


In biochemical oxidation reactions, the oxygen atom added to the alekene is ultimately derived from molecular oxygen, O2.  The biomolecule playing the same role as peroxyacids is flavin peroxide, a derivative of the nutrient riboflavin, or vitamin B2.

flavin hydroperoxide.png


The previous few reactions have been classified as reductions or oxidations, depending on the change in oxidation state of the functional carbons. It is important to remember that whenever an atom or group is reduced, some other atom or group is oxidized, and a balanced equation must balance the electron gain in the reduced species with the electron loss in the oxidized moiety, as well as numbers and kinds of atoms. Starting from an alkene (drawn in the box), the following diagram shows a hydrogenation reaction on the left (the catalyst is not shown) and an epoxidation reaction on the right.



Epoxides may be cleaved by aqueous acid to give glycols that are often diastereomeric with those prepared by the syn-hydroxylation reaction described above. Proton transfer from the acid catalyst generates the conjugate acid of the epoxide, which is attacked by nucleophiles such as water in the same way that the cyclic bromonium ion described above undergoes reaction. The result is anti-hydroxylation of the double bond, in contrast to the syn-stereoselectivity of the earlier method. In the following equation this procedure is illustrated for a cis-disubstituted epoxide, which, of course, could be prepared from the corresponding cis-alkene. This hydration of an epoxide does not change the oxidation state of any atoms or groups.



Oxidative cleavage of double bonds



In determining the structural formula of an alkene, it is often necessary to find the location of the double bond within a given carbon framework. One way of accomplishing this would be to selectively break the double bond and mark the carbon atoms that originally formed that bond. For example, there are three isomeric alkenes that all give 2-methylbutane on catalytic hydrogenation. These are 2-methyl-2-butene (compound A), 3-methyl-1-butene (compound B) and 2-methyl-1-butene (compound C), shown in the following diagram. If the double bond is cleaved and the fragments marked at the cleavage sites, the location of the double bond is clearly determined for each case. A reaction known as ozonolysis accomplishes this useful transformation.



Ozone, O3, is an allotrope of oxygen that adds rapidly to carbon-carbon double bonds. Since the overall change in ozonolysis is more complex than a simple addition reaction, its mechanism has been extensively studied. Reactive intermediates called ozonides have been isolated from the interaction of ozone with alkenes, and these unstable compounds may be converted to stable products by either a reductive workup (Zn dust in water or alcohol) or an oxidative workup (hydrogen peroxide). The results of an oxidative workup may be seen by clicking the "Show Reaction" button a second time. Continued clicking of this button repeats the cycle. The chief difference in these conditions is that reductive workup gives an aldehyde product when hydrogen is present on a double bond carbon atom, whereas oxidative workup gives a carboxylic acid or carbon dioxide in such cases. The following equations illustrate ozonide formation, a process that is believed to involve initial syn-addition of ozone, followed by rearrangement of the extremely unstable molozonide addition product. They also show the decomposition of the final ozonide to carbonyl products by either a reductive or oxidative workup.


Ozonides exist in natural organic compounds, include some important medicines. Artemisinin is a Chinese herbal medicine which has been shown to be effective in the treatment of malaria.


Glycol cleavage reactions

The vicinal glycols prepared by alkene hydroxylation (reaction with osmium tetroxide or permanganate) are cleaved to aldehydes and ketones in high yield by the action of lead tetraacetate (Pb(OAc)4) or periodic acid (HIO4). This oxidative cleavage of a carbon-carbon single bond provides a two-step, high-yield alternative to ozonolysis, that is often preferred for small scale work involving precious compounds.


As a rule, cis-glycols react more rapidly than trans-glycols, and there is evidence for the intermediacy of heterocyclic intermediates (as shown), although their formation is not necessary for reaction to occur.



William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry

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09:27, 21 May 2015


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