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Introduction to Rearrangement Reactions

by JA MES
in OR G AN IC CH E MIS TRY 1 , OR G AN IC RE AC TIO N S

The previous four posts on acidbase, substitution, addition, and elimination covered
the 4 main reactions in organic chemistry I. Now its time
to go beyond those mainstays to introduce a few of the
less common (but still important) reactions you learn in
organic chemistry 1. They will be rearrangements,
radical substitution, and cleavage (oxidative cleavage).
Lets look at rearrangements in this post. As with
everything in this series, the point is not to
understand why just yet, but to be able to see from the
diagrams what bonds are broken and formed. You need
to understand how to read line diagrams. But other than
that no further skills are required. The point here is to be
able to follow the plot to see what is happening. A
later series of posts will go into more detail as
to why things happen, but it takes time to build up that
knowledge.
Rearrangement reactions are really interesting. They
can accompany many of the reactions weve previously
covered such as substitution, addition, and elimination
reactions. In fact, if you dont look closely, sometimes
you can miss the fact that a rearrangement reaction has
occurred. Lets look at a substitution reaction first.

On the top is a typical substitution reaction: were


taking an alkyl halide and adding water. The C-Br bond
is broken and a C-OH bond is formed. If you look at the
table on the right youll see this follows the typical
pattern of substitution reactions.
However if we change one thing about this alkyl halide
move the bromine to C-3 instead of C-2 now when we
run this reaction we see a different product emerge. It is
also a substitution reaction (were replacing Br with OH)
but its on a different carbon. Thats because if you
look closely, you can see there are actually 3 bonds
broken and 3 bonds formed. The C2-H bond broke and
the C3-H bond formed.
Very strange!

This represents a rearrangement reaction when you


see a group move from one carbon to another. Lets
look at another example.
Here we have an addition reaction. On top, nothing
special as with all additions, we break a C-C double
bond ( bond )and form two new single bonds to the
adjoining carbons (H and Cl). But look at the bottom
example. If we use that alkene instead, we find that the
Cl ends up on C3, notC-2. Again, examining the bonds
broken/formed, we see that theres an extra pair of
events: the C3-H bond was broken and the C-2H bond
was formed. In other words, the hydrogen migrated
from one carbon to another. Weird!

Finally, lets look at an elimination reaction. If you take


an alcohol like the one below and add an acid (like
H2SO4, pictured) and help the reaction along with some
heat, you break the C1-OH and C2-H bonds, and form a

new double bond between C1-C2. This is, in other


words, a typical elimination reaction.
But if you take a slightly modified alcohol like the bottom
example (with an extra methyl group on C1) and try the
same reaction, something strange happens again.
Analyzing the bonds broken and formed, theres an
extra bond being broken and an extra bond being
formed here. If you look closely you can see that one of
the methyl groups on C1 (well call it C8) moved over to
C2.

So what can we conclude about rearrangement


reactions?
1. they can accompany many of the reactions were
already familiar with, such as substitution, addition, and
elimination reactions.

2. They involve the movement of an atom (H in the top


two examples, C in the third) from one carbon to
another.

What other insight might we glean from these


examples? Heres two questions.
1. look up, if you dont know already, what primary,
secondary and tertiary alcohols and alkyl halides are.
2. In the substitution reactions and the elimination
reactions, classify every alcohol (or alkyl halide)
according to whether it is primary, secondary or tertiary.
Notice any difference between the normal cases and
the rearrangement cases?

For more detail on rearrangement reactions, start


here: Rearrangement Reactions (1) Hydride Shifts
Next Post: Introduction To Free-Radical Substitution
Reactions

Rearrangement Reactions (1) Hydride Shifts


by JA MES

in AL CO H OL S , A LK YL HA LI DE S , O R GA NI C C HE MI S TRY 1 , O R GA NI C R EA C TI O NS

For nucleophilic substitution, the pattern of bonds that


form and break is pretty straightforward. You break C(leaving group) and you form C-(nucleophile). A straight
swap. But every once in awhile you might see a weird
substitution reaction. If you look closely at the pattern of
bonds formed and bonds broken in the second reaction
below, theres an extra set!

In other words its a substitution reaction where the


hydrogen has moved. We call these movements
rearrangements, for reasons that will become clear
shortly.

The big question is, whats going on? How did this
happen?
As it turns out, reactions that go through
carbocations can sometimes undergo
rearrangements. And looking back at substitution
reactions, recall that theSN1 reaction goes through a
carbocation intermediate. In this post well go through
when youll expect to see a rearrangement reaction.
Lets think back to carbocations. Theyre carbon atoms
with six electrons bearing a positive charge. In other
words, theyre electron deficient 2 electrons short of a
full octet. So it would make sense that carbocations
become more stable as you increase the number of
electron donating groups attached to them. Alkyl
groups are a perfect example. Thats why carbocation
stability increases as you go from primary to secondary
to tertiary.

(Its also worth pointing out that carbocations are also


stabilized by resonance, which allows the positive
charge to be delocalized or spread out over a greater
area on the molecule.)
So what does this have to do with rearrangements? As it
turns out, if a situation exists where an unstable
carbocation can be transformed into a more stable
carbocation, a rearrangement is possible.

One rearrangement pathway where an unstable


carbocation can be transformed into a more stable
carbocation is called a hydride shift. Look at the
diagram below.

In this reaction we have a secondary carbocation on the


left hand side. In this rearrangement reaction, the pair of
electrons in the C-H bond is transferred to the empty p
orbital on the carbocation. In the transition state of this
reaction, theres a partial C-H bond on C3 and a partial
C-H bond on C2. The transition state here is kind of
like that split second in a relay race where one
sprinter is passing the baton to another sprinter and
they both have their hands on it. Then, as the C2-H
bond shortens and the C3-H bond weakens, we end up
with a carbocation on C3 (a tertiary carbocation) in the
product which is more stable.
Note that we only need one arrow to show this
occurring!
Here are some examples of allowed rearrangement
reactions. Notice how were always going from a less
substituted carbocation to a more substituted
carbocation. One exception is at the very bottom; the
rearrangement is favorable because the new
carbocation is resonance stabilized.

Now were ready to show how the rearrangement


reaction occurs with the SN1. Recall that the first step in
the SN1 is that the leaving group leaves to give a
carbocation. In the case below, the carbocation that is
formed is secondary, and theres a tertiary carbon next
door. Therefore, a rearrangement can occur to give the
more stable tertiary carbocation, which is then attacked
by the nucleophile (water in this case). Finally, the water
is deprotonated to give the neutral alcohol. So this is an
example of an SN1 reaction with rearrangement.

Ive given some more examples of SN1 reactions with


rearrangements below. See if you can draw the
mechanisms! In the next post well talk about a slightly
different rearrangement pathway with substitution
reactions.

Next Post: Rearrangement Reactions (2) Alkyl


Shifts

Rearrangement Reactions (2) Alkyl Shifts


by JA MES

in OR G AN IC CH E MIS TRY 1

In the last post we saw how certain carbocations can


sometimes rearrange (through hydride shifts)to give
more stable carbocations.
However, sometimes there are situations where a
hydride shift would not lead to a more stable
carbocation, such as in this case. If a hydride shift
occurred, wed be going to a less stable (primary)
carbocation.

You might note something with this example, however:


it is possible for a more stable tertiary carbocation to be
formed if an alkyl group migrates instead!

The most common situation where alkyl shifts can occur


is when a quaternary carbon (thats a carbon attached to
4 carbons) is adjacent to a secondary carbocation. How
does this work? Well, the pair of electrons from the C-C
bond can donate into the empty p orbital on the
carbocation (side note: this means they have to be
aligned in the same plane). In the transition state, there
are partial bonds between the carbon being transferred
and each of the two adjacent carbon atoms. Then, as

one bond shortens and the other lengthens, we end up


with a (more stable) tertiary carbocation.

Rearrangements can potentially occur any time a


carbocation is formed. That includes SN1 reactions (and
as well later see, elimination and addition reactions).
Heres an example of an SN1 with an alkyl shift (note
that the CH3 groups here are just shown as lines).

It doesnt always have to be a methyl group that moves.


One interesting example is when a carbocation is
formed adjacent to a strained ring, such as a

cyclobutane. Even though the CH3 could potentially


migrate in this case, its favorable to shift one of the alkyl
groups in the ring, which leads to ring expansion and
the formation of a less strained, five-membered ring.
Heres an example of an SN1 where an alkyl shift leads
to ring expansion.

Having gone through two types of rearrangements in


substitution reactions, the next series of posts will cover
a different class of reactions: elimination reactions.

Molecular Rearrangement
https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/Questions/Rearang/rng
prb1.htm
Six reactions in which molecular rearrangement takes place are shown below. Formulas and some
other information about the products are provided. Draw a structural formula for each of the
designated products.
To draw a formula use the Drawing Window on the right below. Do not draw hydrogen atoms, and
do not attempt to indicate stereochemical configurations. When you are finished, check your answer
by pressing the appropriate Check Product button.

A response to your answer will appear in the evaluation window below.