Carbocations

Capture nucleophile

Deprotonation

Rearrangement

An Alternate Ionic Substitution Mechanism

Generic SN2 mechanism:

Can you identify the assumption?

Carbon-Nuc bond formation simultaneous with carbon-LG bond scission.
Concerted: A mechanism in which all bond changes occur simultaneously.

Alternate mechanisms: Asynchronous (nonconcerted) bond changes.

Alternate #1: Carbon-nuc bond formed before carbon-LG bond scission.

This alternate mechanism is / is not possible.

 An Alternate Ionic Substitution Mechanism
Alternate #2: Carbon-LG bond scission before carbon-nucleophile bond formation.

Six electrons on carbon

A carbocation

Intermediate: A species which is not starting material, product, or transition state.

Carbocations are common intermediates in organic mechanisms.
Example: Ionization of dimethylallyl pyrophosphate in steroid biosynthesis.

Dimethylallyl pyrophosphate Carbocation

Carbocations: Structure

What is the structure of a carbocation?

Three attachments causes causes Carbon is sp2

Trigonal planar
on carbon pz orbital is empty
 Carbocations: Structure vs. Stability
Degree of substitution
How does carbocation structure influence carbocation stability?
Explain this stability trend:

Methyl carbocation 1o Carbocation 2o Carbocation 3o Carbocation

No C-C+ bonds One C-C+ bond Two C-C+ bonds Three C-C+ bonds

Increasing stability
Increasing number of C-C+ bonds

Rationale: C+ is electron deficient

Alkyl group is weak electron donor

+CH very very unstable never appears in Chem 14D reactions.

3

Carbocations: Structure vs. Stability

Resonance adjacent lone pairs

Select the more stable carbocation: Both are methyl carbocations

In general... Delocalizing the carbocation positive charge stabilizes the carbocation.

X = O, N, F Resonance highly significant

X = S, Cl, Br, I Resonance less significant
Maximizing full octets outweighs position of formal charge.
Review resonance from Chem 14C if needed.
 Carbocations: Structure vs. Stability
Resonance adjacent pi bonds

Select the more stable carbocation: Both are 1o carbocations

Carbocation resonance also possible with triple bonds and benzene rings:

One more contributor

X
Three more contributors No pi bond resonance

Student exercise: Draw resonance contributors and hybrids.

Carbocations: Structure vs. Stability

What happens when degree of substitution and resonance compete?

Select more stable carbocation:

Degree of substitution:
Resonance:

A paradox!
Observation of many carbocation stabilities reveals a general rule:
Resonance from one pi bonds outweighs stability from one alkyl group.
Therefore: Secondary with resonance more stable than tertiary without resonance.
 Carbocations: Structure vs. Stability
Why is carbocation stability important?

More stable causes lower / higher causes faster / slower

carbocation G to form carbocation formation

Example: In steroid biosynthesis DMAPP and IPP join via a carbocation.

Which molecule ionizes to form this carbocation? DMAPP IPP

Tertiary with resonance

DMAPP

X Primary without resonance

IPP

Conclusion: More stable carbocation from DMAPP IPP. Faster ionization: DMAPP IPP.

Carbocation Fates
Now that I have a carbocation, what do I do with it?
How do carbocations react?
What is a carbocation's motivation?

Positive formal charge

Open octet
Electron deficiency

Carbocations react in ways to ...reduce or resolve their electron deficiency.

...become more stable.

Three common ways in which carbocations react: The Carbocation Fates.

 Carbocation Fates
Carbocations desire to become more stable.

Carbocation desires electron pair to fill octet.

Electron pair can be provided by ________________________________.

Carbocation Fate #1: Capture a nucleophile

Carbocations are desperate and not fussy.

Even weak nucleophiles are easily captured.

Carbocations are often formed in the absence of strong nucleophiles.

Carbocation Fates
Carbocations desire to become more stable.

Carbocation desires electron pair to fill octet.

Electron pair can be provided by ________________________________.

Carbocation Fate #2: Be deprotonated; form pi bond

Carbocations are desperate and not fussy.

Even weak bases can deprotonate a carbocation.

Carbocations are often formed in the absence of strong base.

 Carbocation Fates
Carbocations desire to become more stable.

Carbocation desires electron pair to fill octet.

Electron pair can be provided by ________________________________.

1,2-H shift 1,2-CH3 shift

Carbocation Fate #3: Carbocation rearrangement

Carbocation Fates
Carbocation rearrangement is an equilibrium process.
Not all rearrangements are equally likely, or even allowed.

Increase in stability
Very common

No change in stability
Somewhat common

Decrease in stability
Possible but uncommon
 Carbocation Fates
Some rearrangement restrictions...
Only groups adjacent to C+ can migrate:

1,2-CH3 shift -- allowed

1,3-CH3 shift -- forbidden

Only carbon groups and hydrogen atoms can shift:

1,2-OH shift -- forbidden

Carbocation Fates
What happens when multiple fates are possible?

Capture nucleophile

Deprotonation

Rearrangement

Carbocations are __________________ and not ___________________.

Reactivity-selectivity principle: More reactive species are less selective.
So which occurs? Capture nucleophile Deprotonation Rearrangement

Extensive carbocation tutorial available on course web site.