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Alkene Addition Pattern #2: The “Three-Membered Ring” Pathway

The “Three-Membered Ring” Pathway In The Mechanisms of Reactions of Alkenes

In the last post we walked through a proposal for how the bromination of alkenes works and showed that it adequately explains many of the experimental observations made for this reaction. Namely, the reaction proceeds with anti addition of substituents across the alkene, and (where relevant) the reaction proceeds with Markovnikov regioselectivity. These observations are best explained through the intermediacy of a “bromonium ion”.

Taking bromination of alkenes as a starting point, we might ask: “do variants of this mechanism operate for other reactions of alkenes as well?”

The answer is yes!

Chlorination of Alkenes

Take, for example, the chlorination  of alkenes. The products of this reaction has identical patterns of stereoselectivity and regioselectivity to those of bromination. Therefore we might surmise that they proceed through the same type of reaction intermediate! [This intermediate is called the “chloronium ion”]

Iodination of Alkenes

This is also the case for iodination reactions, which proceed through the “iodonium ion”:

Chlorohydrin Formation

This also applies to reactions where the intermediate chloronium ion is trapped with solvent (water in this case). After deprotonation of R–OH+ to give R–OH,  the product is referred to as a “chlorohydrin”.

Note that bromohydrin and iodohydrin formation work exactly the same way and if you merely replace “Cl” with either of those halogen atoms you’ll obtain the indicated product.

“Haloether” Formation

As described in the last few posts, what’s notable about bromination is that by using a solvent which can act as a nucleophile, we can obtain products which incorporate that solvent. For example by using an alcohol as solvent, we obtain the following “chloroetherification” product. It likewise proceeds through the exact same mechanism described above.

Furthermore, these reaction pathways are not confined to the dihalogens Cl2, Br2, and I2 [nor F2, the Tiger of Chemistry, which is a very difficult beast to keep on its leash]. And a good thing too, since Cl2 and Br2 are to various extents vile and inconvenient to work with.

Chlorohydrin Formation Using N-Chloro Succinimide

A convenient source of “electrophilic” chlorine is the crystalline salt N-chlorosuccinimide (NCS), an innocuous appearing white crystalline solid. Alkenes react rapidly with NCS to form chloronium ions, which can then be intercepted to form a variety of useful products by analogy to those shown above. With the exception of this more convenient source of halogen, the reaction is otherwise the same. N-bromosuccinimide (NBS) and N-iodosuccinimide (NIS) likewise find use.

Moving beyond the halogens, are there other reagents that form these cyclic intermediates? Why, yes indeed.


When alkenes are treated with mercury (II) salts (such as mercuric acetate) in the presence of water or alcohols, we obtain products with the same pattern of stereochemistry and regiochemistry that we’re accustomed to seeing by now. What’s a likely intermediate here? A three-membered ring called the “mercurinium ion”.

Organomercury compounds find very little application in themselves, but can be used as intermediates in subsequent reactions. To replace mercury with hydrogen, sodium borohydride (NaBH4) is added. In this case,  rather than being “anti” , the stereochemistry of this reaction ends up being a wash: treatment with NaBH4 leads to cleavage of the C-Hg bond and formation of a free radical. The free radical can react from either face with hydrogen, leading to scrambling of the stereocenter. Mechanism link.

How many other reactions go through this type of mechanism? There is actually a sizable list. For instance, there are electrophilic sources of sulfur and selenium that can likewise form three membered cationic rings just like those we’ve seen; we won’t go into those.

A Non-Obvious Cousin: Protonated Epoxides

One last example that is worth going into is one that might not immediately seem obvious: protonated epoxides.

Treatment of an epoxide with acid leads to a positively charged intermediate that resembles a bromonium ion. As you might guess, the nucleophile attacks the backside of the most substituted carbon and the resulting product has anti stereochemistry. Just as we’ve seen numerous times above.

The lesson for this very long post from today is that one can group together a sizable number of different reactions by identifying their common mechanism. Just as there is a family of reactions that pass through the carbocation pathway, there is likewise a “family” of reactions that pass through a three-membered ring.  Instead of learning a dozen different mechanisms, we merely learn one – and merely change the actors to suit the occasion.

NEXT POST – Hydroboration of Alkenes

P.S. Besides the dihalides, there are also such things as mixed dihalides, such as iodine monochloride. We have all the tools at our disposal to answer how this reaction might proceed. What do you think the product is?

[answer in comments]


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