Rearrangements in Alkene Addition Reactions
Last updated: November 18th, 2022 |
Carbocation Rearrangements In Alkene Addition Reactions
In exploring reactions that proceed along the carbocation pathway, every once in awhile you might see an example of an addition reaction that looks a little… strange. The alkene is gone, two new bonds have formed, but the positions of the new bonds is a little out of the ordinary. Like in this example!
If you tally up the bonds that form and the bonds that break, we notice that there is an extra set of C-H bond forming/breaking events.
Table of Contents
- What Are Carbocation Rearrangements?
- Hydride Shifts In Alkene Additions, Step 1: Attack Of Acid By The Nucleophile
- The Key Rearrangement Step: Hydride Shift
- Step Three: Attack Of Nucleophile On The Carbocation
- Alkene Addition Reactions With Alkyl Shifts
- Alkene Addition Reactions With Ring Expansion
- (Advanced) References and Further Reading
[If you haven’t seen rearrangements before, read this. If you have, you can skip to the “walkthrough of an addition with rearrangement” section.] Rearrangements can accompany any reaction that proceeds through a carbocation, be it substitution (SN1), elimination (E1) or, as we’ve just seen, addition.
Bearing less than a full octet of electrons, carbocations are unstable intermediates. Being electron-poor, the stability of a given carbocation greatly depends on the extent to which the atoms adjacent to it can donate electron density, either through resonance, “inductive effects”, or (although rarely taught) “hyperconjugation”.
Rearrangements occur when an entire bonding pair of electrons migrates to a carbocation from one of its neighbors. This will be favorable when a new, more stable carbocation is formed. The bonding pair in question may be attached to a hydrogen or alkyl group. Migrations of a hydrogen with its lone pair are called “hydride shifts”; migrations of a carbon atom with its lone pair are called “alkyl shifts”.
Note that the carbocation that’s been formed is a secondary carbocation, and it’s adjacent to a tertiary carbon.
In this next step, the lone pair in the C-H bond migrates from the tertiary carbon to the secondary, forming a new (tertiary) carbocation. The driving force for this reaction is formation of the more stable carbocation.
Note how it’s just one arrow we’re drawing here! The same arrow shows C-H bond breakage and C-H bond forming.
Rearrangements can also occur with alkyl shifts, as seen in the example below. Note again that the rearrangement step is represented by just one curved arrow!
Finally, one of the cases that students often find very difficult is in recognizing reactions that occur with rings (ring expansion or ring contraction). Although perhaps difficult to see, in fact it proceeds through exactly the same mechanism as in the cases above. Note again that we’re depicting the rearrangement reaction with a single curved arrow. [Hint – if you’re doing this on your own, it might help to draw the ugly version first].
So why is it that the carbon from the ring migrates, and not the CH3 as before? A fair question. Migration of the CH3 would indeed produce a tertiary carbocation. However, migration of the CH2 from the ring not only produces a tertiary carbon but incrases the size of the ring from 4-membered to 5-membered, which relieves considerable ring strain present in the cyclobutane ring (worth about 26 kcal/mol).
NEXT POST: Bromination of Alkenes – How Does It Work?
- Ueber die Beziehung der Pinenhaloïdhydrate zu den Haloïdanhydriden des Borneols
Georg Wagner, W. Brickner
Ber. 1899, 32 (2), 2302-2325
The oldest examples of these rearrangements are in the pinene series. Wagner showed these rearrangements occur in conversions of pinene to bornyl compounds.
- Über die Gleichgewichts‐Isomerie zwischen Bornylchlorid, Isobornylchlorid und Camphen‐chlorhydrat
Hans Meerwein and Konrad van Emster
Ber. 1922, 55 (8), 2500-2528
Prof. Hans Meerwein extended Wagner’s work to non-terpene series, and came up with the crucial insight that it proceeded through a carbonium ion – a very controversial insight at the time! Crucial experiment was finding rate was dependent on solvent polarity. Rate order was SO2 > MeNO2 > MeCN > PhNO2 > PhCN > PhOMe > PhBr > EtBr > PhCl > C6H6 > pet ether > ether. Furthermore, he found that certain acids considerably accelerated the rearrangement of camphene hydrochloride to isobornyl chloride. Alkyl migrations in carbocations are often called “Wagner-Meerwein” rearrangements after Georg Wagner and Prof. Hans Meerwein, who studied them more rigorously.
- Mechanism of substitution at a saturated carbon atom. Part XXXII. The rôle of steric hindrance. (Section G) magnitude of steric effects, range of occurrence of steric and polar effects, and place of the Wagner Rearrangement in nucleophilic substitution and elimination
I. Dostrovsky, E. D. Hughes, and C. K. Ingold
J. Chem. Soc. 1946, 173-194
Prof. Ingold formalized rules for carbocations:
1) It is necessary for rearrangement that initial bond breakage result in an atom with an incomplete octet
2) The system will only rearrange if the free energy change is in the right direction (i.e. the carbocation being rearranged to should be more stable, e.g. secondary -> tertiary).
This tied together SN1, E1, alkene addition with Wagner-Meerwein shifts in a unified framework.
- Communications TO THE EDITOR
The Journal of Organic Chemistry 1962, 27 (5), 1926-1932
Rigid steroid and diterpenoid systems show addition reactions where multiple hydride and alkyl shifts can occur. One example is dihydroipimaric acid.
- The constitution and stereochemistry of euphol
H. R. Barton, J. F. McGhie, M. K. Pradhan, and S. A. Knight
J. Chem. Soc. 1955, 876-886
Euphenol, which is similar to lanosterol, also undergoes addition via a carbocation intermediate which can undergo successive hydride and alkyl shifts.
- The Structures of the Triterpenes Friedelin and Cerin
E. J. Corey and J. J. Ursprung
Journal of the American Chemical Society 1956, 78 (19), 5041-5051
The path from Friedelin to Cerin is a crazy series of fun rearrangements!
- Total synthesis of (±)-isocomene and related studies
Michael C. Pirrung
Journal of the American Chemical Society 1981, 103 (1), 82-87
The rearrangement of vinyl cyclobutane opening to cyclopentane is accompanied by relief of ring strain, and this paper shows that can be applied fruitfully in sesquiterpene synthesis.
- The Addition of Hydrogen Bromide to Simple Alkenes
Hilton M. Weiss
Journal of Chemical Education 1995, 72 (9), 848
A simple experiment suitable for undergraduate organic chemistry laboratory courses that demonstrates that it is possible for the intermediate carbocation to rearrange and give different products.