Aldehydes and Ketones

Chapter 16
 Structure
Aldehydes Ketone

O Carbonyl O
group

R H R R

sp2
2-pentanone
O
pentanal
O
 Examples of Naming
O OH
O

O
pentan-2-one O
3-oxopentanal

O O
2-(1-hydroxyethyl)pentanal
CHO

CH3
H CHO

H CO2H
CH3
benzaldehyde
2,3-dimethyl-4-oxobutanoic acid
(E)-3-(but-1-enyl)hexane-2,4-dione
 Resonance
O O

 
O
result
Extension of resonance

O O
 Boiling points
For compounds of comparable molecular weight…

Alkanes, ethers < aldehydes, ketones < alcohols < carboxylic acids

Dipole-dipole Hydrogen Bonding

Dispersion
Forces

Water Solubility
Ketones and Aldehydes, like ethers, can function as hydrogen bond
acceptors and smaller compounds have significant water solubility.
 Recall Preparation from Alcohols
OH OH
Can also be
done using Na2Cr2O7

KMnO4 in base Be sure you can

with heat or HO
acid, 35 deg.
O balance this
bleach in acid kind of reaction.
solution CO2H
CH2OH
(HOCl).
Use PCC to limit oxidation of primary alcohol to the aldehyde.
Secondary are oxidized to ketone.
Primary alcohol
PCC
RCH2OH RCH=O

Secondary
PCC
R2CHOH R2C=O
 Preparations, con’d
• Reaction of acid chloride and Gilman
O

R OH
SOCl2
O
Na2Cr2O7
O
RCH2OH
R Cl

R R'

R' 2CuLi

1. Li
But where do we
get these??
R'X 2. CuX
 Note that we have two possible disconnects available

HOCH2R

R'OH

+ R'X

O HO R

R' R
O

+ RX

R' OH

ROH
HOCH2R'
 Example: Prepare 2-butanone from ethyl alcohol

Requirement to start with ethanol suggests a disconnect into two carbon fragments.

CH3CH2OH

O
Done!
CH3CO2H + CH3CH2X

via Gilman and

acid chloride
 Aldehydes from carboxylic acids

Reduction

O SOCl2 O LiAlH(OC(CH3)3)3 O

R OH R Cl R H

And from alcohols, as before:

PCC Oxidation

RCH2OH RCHO
 A Common Sequence
PCC
RCH2OH RCHO OH

PX3 Mg R R'
R'OH RX R'MgX

Na2Cr2O7

Observe these parts at this moment. R R'

 Reactions
Addition of a nucleophile: Nucleophilic Addition

Good nucleophile, usually basic

O
O O

+ Attack of
Nu: -
Nu Nu nucleophile
tetrahedral intermediate
occurs on both
sides of carbonyl
group.

OH
Produces both
OH
configurations.
+

Nu Nu

Overall: H – Nu was added to carbonyl group double bond.

Notice that the CO bond order was reduced from 2 to 1. The addition reduced the bond
order. We will use this idea later.
 Reaction can also be done in acid environment.
Nucleophiles not expected to be as strong (why?) but the oxygen may
become protonated making the carbonyl a better electrophile
(why?).

O acid OH
OH OH

Nu: Nu Nu

Very electronegative,
protonated oxygen. Pulls
the pi electrons into itself
strongly.

Problem: If there is too much acid present the nucleophile may become
protonated, deactivating it
 Addition of Grignard (Trumpets Please)

Recall the formation of a Grignard and its addition to an oxirane

O

Mg   OMgX

R-X R-Mg-X
ether
R
O
Carbonyls may be added to
OMgX OMgX
in same way…
Mg   +
R-X R-Mg-X
ether R R

If a new chiral center is mild acid

created both configurations
will be produced. OH OH

R R
 Common Reactions of Grignards
R2R'COH ROHRXRH(D) OH
a tertiary alcohol R-H Both of these
reactions extend
acid, O R carbon chain &
Examine reaction R'CO2Et weak acid
with ester further. an ester primary alcohol keep -OH
O
functionality at
ROH + R’CH2OHRX + R’CO2HR2C(OH)R’ end of chain.
O Can extend
R-Mg-X
H H further.

R' R'' RCH2OH

O
CO2 primary alcohol

R' H
RR'R''C-OH
tertiary alcohol

ROH + R’R”CHOH RCHR' secondary alcohol RCO2H

carboxylic acid
RX + R’R”CO RR’C (OH)R” OH

ROHRXRCO2H

ROH + R’CH2OHRX + R’CHORCH(OH)R’

 Grignard Reacting with an Ester.
Look for two kinds of reactions.

O O
O OMgX

R-Mg-X R-Mg-X

R' OEt R' R R' R

R' OEt R R
Substitution
Any alcohol
will do EtOH
But where does an ester
here. come from? OH
R'COCl Acid
chloride
R' R
R
SOCl2
Perhaps this carboxylic acid
Addition
comes from the oxidation of a
R'CO2H
primary alcohol or reaction of
a Grignard with CO2.
Synthetic Planning… Use of epoxides and
carbonyls offer different disconnect sites. Pattern
1. RMgX HO HO-C-C-R
O
2. H2O, HCl
epoxide
R

Nucleophile
New bond.
Disconnect site.

O OH
R-Mg-X New bond. Pattern
carbonyl Disconnect
R site HO-C-R

Want this to be
the nucleophile
(Grignard).
 Patterns to recognize: carbonyl vs
oxirane
We can create the following fragments of
target molecules by using an
organometallic (carbon nucleophile)
reaction with a carbonyl

O RMgX dil. acid OH

The difference is the

extra CH2 when using
R
an oxirane.
reaction with a oxirane

O RMgX dil. acid OH

R
 Synthetic Planning…

Three different disconnects possible

OH
Give synthetic O

routes to + R3-Mg-X
C
R1 R2
R1 R3
R2

+ R2-Mg-X
O R1 R3
+ R1-Mg-X
R2 R3

If none of the Rs are H then these three synthetic

routes may be available.
 Example: Synthesize from ethanol
CH3CH2OH

CH3CH2X
O

OH

Done
OH
MgX CH3CO2Et
2

O
CH3CO2H CH3CH2OH
CH3CH2MgX CH3CH2OH

Preliminary Analysis
•Hmmm, even number of carbons, at least that is good; ethanol is a two carbon
molecule.
•Now the problem is to divide it up into smaller fragments.
•Ether linkage is easily constructed. Williamson.
•Two butyl groups attached to the central 2 carbon fragment. Grignard + ester.
 Bisulfite Addition

O
O OH

S S
S HO O O O
HO O
O O
O

Addition product.

Practical importance: liquid carbonyl compounds can be difficult to purify. The

bisulfite addition products will be crystalline and may be recrystallized.
 Addition of Organolithium
Compounds to Carbonyls
Generally the reactions are the same as for Grignards but the lithium
compounds are more reactive (and more difficult to handle).
O
O OH

Br Li

Li
mild acid

bromocyclohexane
Decreased reactivity of
electrophile due to steric
hindrance to attack. So we
used the alkyl lithium instead of
a Grignard.
 Nucleophiles derived from terminal alkynes
For example, once
formed, the new
alkynyl alcohol can be
hydrated in two ways,
Markovnikov and anti
Markovnikov.
Carefully observe the
structure of the
products, the
relationship of the OH
and the carbonyl.
Can do all the reactions of an
alkyne and an alcohol. But
remember that we have two
acidic groups: the more acidic
OH and the less acidic terminal
alkyne. We discussed this
problem earlier.
Note that the
regioselectivity
used here is only
effective if this
alkyne is terminal.
Otherwise get a
mixture.
 Addition of hydrogen cyanide

basic

Think of what the mechanism should be….

pH issue.
Slightly basic
media so that
HCN has
partially ionized
to cyanide ion,
Followed by protonation of the alkoxide ion (perhaps by the actual
unionized HCN). nucleophile.
 Follow-up reactions on the
cyanohydrins… H2O
R

N
RHC
acid catalysis
dehydration
We saw this hydrogenation before.
O NaCN dil acid OH
OH
H2
R N
NH2
R CH2R
CH2R catalyst R
CH2R
Hydrolysis. Acid, heat
or
base, heat OH

CO2H
R
CH2R
 Let’s see what we can do with the mechanism of the
hydrolysis of the nitrile group to a carboxylic acid.
Overall
aq. acid, heat + NH3
R
R
CO2H

The action is at the nitrile group, CN --> CO2H.

But how does a nitrile group behave? What could be happening?
We are breaking the CN bond; bond order goes from 3 to 0. Probably stepwise.
Chemically speaking: the nitrogen of the nitrile is basic (lone pair) and can
be protonated. This makes it a better electrophile (cf. carbonyl). Multiple
bond can undergo addition (cf. carbonyl) reducing bond order.
Goal: Break the C to N bonding and create C-O bonds.
Considerations: neither the electrophile (RCN) nor the nucleophile (water) is very
reactive. Since we are in acid protonate the CN group to make it a better electrophile.
Then attack it with the water nucleophile to add water. This results in reduction of C-N
bond order and creation of C to O bonds .
Again, we are in acid environment. Let’s protonate something….
Protonate the multiple bonded N atom to make better electrophile and attack with
the nucleophile, water.
Note the bonding pattern here. We have seen it before.
R acid
R
N
HO NH
similar to
NH HO CH2
which tauermerizes in acid or base, keto-enol

HO CH2
O

R R R R

+ H+ + H+
NH
NH NH NH2
H2O HO O
HOH

What have done so far? Reduced the CN bond order from 3 to 2 and added one
O to the C. Moving in the right direction!
Want to reduce the CN bond order to zero and introduce more O on the C. Keep
going! To induce the water to attack again (adds another O) need to increase
the reactivity of the electrophile. Protonate again!! On the O.
 HOH
R acid
R

NH2 OH2
O R
NH2
O

H NH2
Initial equilibrium with acid HO

Now want to get rid of the NH2. We have all the O’s we need.
We know what we have to do. Have to get the N protonated to make
it a good leaving group.
OH2
H
R
+ NH3
reposition the H+ O
NH2 R
HO
O
R
NH3
HO

HO

Done.
 Wittig Reaction
O

H I Bu-Li R R
PPh3
or NaH
Substitution Elimination R R

Example, synthesize CHCH3

or combine them the other way…

 Wittig Reaction Mechanism
H
H Acidic
I
hydrogen
Ph3P
Ph3P: +
Nucleophilic substitution Nucleophilic
H
strong base, BuLi center
Ph3P
Ph3P Phosphonium ylide
R R
O O
O
R R

+ Ph3P Ph3P
Ph3P R R

oxaphosphetane
betaine
R
R R
O
R

Ph3P Ph3PO

oxaphosphetane
Friedel Crafts Acylation

R O
O

R Cl

AlCl3

And then all the

reactions of ketones…
Formation of Hydrates, carbonyls
and water.

Carbonyl side of equilibrium is usually favored.

 Hemiacetals and Acetals, carbonyls and alcohols

Addition
reaction.
(Unstable in
Acid; Unstable
in base)

(Unstable in
Acid; Stable in
base)

Substitution reaction
 Formation of Hemiacetals, catalyzed by either
acid or base. Let’s do it in Base first.
But first let’s take stock.
We have an addition reaction.
Just mixing a carbonyl and an
alcohol
Use Basedotonot cause a
reaction.
set-up good
necleophile.
One of them must be made a
better reactant.
Carbonyl can be made into a
Poor nucleophile Good nucleophile
better electrophile by
protonating in acid.
Alcohol can become a better
nucleophile in base by An addition of the
ionization. alcohol to the carbonyl
has taken place. Same
mechanism as
discussed earlier.
hemiacetal
 Alternatively, hemiacetal formation
in Acid
Protonation of
carbonyl (making the
oxygen more
electronegative)

Attack of the (poor)

nucleophile on (good)
electrophile.

Deprotonation

Overall, we have added

the alcohol to the
carbonyl.
 Hemiacetal to Acetal, Acid Only

Protonate the hemiacetal,

setting up leaving group.

Departure of leaving
group.

Attack of
nucleophile

Substitution
Deprotonation
reaction, cf
S 1.
 Equilibria
Generally, the hemiacetals and acetals are only a minor component of an
equilibrium mixture. In order to favor formation of acetals the carbonyl
compound and alcohol is reacted with acid in the absence of water. Dry
HCl) The acetals or hemiacetals maybe converted back to the carbonyl
compound by treatment with water and acid.
An exception is when a cyclic hemiacetal can be formed (5 or 6 membered
rings).
The alcohol
Hemiacetal of D-Glucose
The carbonyl

Try following
the
stereochemistry
here for yourself

The hemiacetal can form with two different configurations at the carbon of the
carbonyl group. The carbon is called the anomeric carbon and the two
configurations are called the two anomers. The two anomers are
interconverted via the open chain form.
Stabilities of the Anomers…
Here note the alternating up-down relationships.

More stable  form, with the

OH of the anomeric carbon is
equatorial

Less stable  form.

Here see the cis relationship of these two OH groups, one

must be axial.
 Acetals as Protecting Groups
Synthetic Problem, do
E
Target molecule
a retrosynthetic analysis
N

Form this bond by reacting a nucleophile with an

electrophile. Choose Nucleophile and Electrophile
centers.
Grignard would
The nucleophile react with this
could take the carbonyl.
form of an
Br-Mg
organolithium or
a Grignard
reagent. The
electrophile
would be a
carbonyl. Do you see the problem with
the approach??
 Use Protecting Group for the carbonyl…
Acetals are stable (unreactive) in neutral
and basic solutions.
Create
acetal as
protecting
group. protect

Now create
Grignard and then
react Grignard with
react
the aldehyde to
create desired
bond.

Remove protecting
group.
deprotect
Same overall steps as when we used
silyl ethers: protect, react, deprotect.
 Tetrahydropyranyl ethers (acetals)
as protecting groups for alcohols.
Recall that the key step in forming
the acetal was creating the
carbocation as shown…
There are other ways to create carbocations……
Recall that we can create This resonance stabilized
carbocations in several carbocation then reacts with an
ways: alcohol molecule to yield the acetal.
1. As shown above
by a group leaving. An acid
2. By addition of H+
to a C=C double bond as
shown next.
This cation can now react with an alcohol
to yield an acetal. The alcohol becomes
part of an acetal and is protected.
 Sample Problem
Provide a mechanism for the following conversion

O
HCl/H2O
HO OH

O O

OH

First examination:
have acid present and will probably protonate
Forming an acetal. Keep those mechanistic steps in mind.

Ok, what to protonate? Several oxygens and the double bond. Protonation of an
alcohol can set-up a better leaving group. Protonation of a carbonyl can create a
better electrophile.
We do not have a carbonyl but can get a similar species as before.
 Strongly electrophilic center, now can do
The protonation of the C=C addition to the C=O
O O O
H+

H
O O

Now do addition, join the molecules

OH

HO
HO OH
Product
O O O

Now must open 5 membered ring here. Need to set-up leaving group.

HO HO

H+ H
O O O O
Leaving group leaves….

HO HO HO

H H H
O O O O O
O

Followed by new ring closure.

HO

O O O O
H H
O O

OH OH

Done. Wow!
 Sulfur Analogs

Consider formation of acetal O

OH OH
O O

dry HCl
acetaldehyde
ethanal

Sulfur Analog
O
SH SH
S S

dry HCl
acetaldehyde
ethanal dithiane
 The aldehyde hydrogen has been made acidic

Bu Li
+ BuH
S S S S

Why acidic?

Sulfur, like phosphorus, has 3d orbitals capable of accepting electrons: violating octet
rule.
filled carbon p orbital

S S S S

empty sulf ur 3d orbital

 Recall early steps from the Wittig reaction discussed earlier

H
H I

Ph3P
Ph3P: +

H
strong base, BuLi
Ph3P
Ph3P

This hydrogen is acidic.

Why acidic? The P is positive and can accept charge from the negative carbon
into the 3d orbitals

PH
Some Synthetic Applications
 Umpolung – reversed polarity

What we have done in these synthetic schemes is to reverse the polarity of the
carbonyl group; change it from an electrophile into a nucleophile.

O
O CN

CN

electrophile

O O

OH

O
S S

nucleophilic

Can you think of two other examples of Umpolung we have seen?

Nitrogen Nucleophiles
 Mechanism of Schiff Base
formation
Attack of nucleophile
on the carbonyl
Followed by transfer of
proton from weak acid
to strong base.

Protonation of –OH
to establish leaving
group.

Leaving group
departs, double
bond forms.
Hydrazine derivatives
 Note which nitrogen is nucleophilic

O
H2N
N NH2 H2N
H
N NH2
H

Nucleophilic nitrogen
Favored by resonance
Less steric hinderance
 Reductive Amination

Pattern:
R2C=O + H2N-R’   R2CH-NH-R’
 Enamines
Recall primary amines react with carbonyl compounds to give Schiff bases
(imines), RN=CR2.

Primary amine

But secondary amines react to give enamines

See if you can write the mechanism for the reaction.
Secondary Amine
 Acidity of  Hydrogens
 hydrogens are weakly acidic

Weaker acid than alcohols but

stronger than terminal
alkynes.

Learn this table….

 Keto-Enol Tautomerism
(Note: we saw tautomerism before in the hydration of alkynes.)

Fundamental process
acid or base
O catalysis HO

CH3 CH2

keto form enol form

usually small component

Mechanism in base:
O :OH- O O HO
H-O-H
CH3 CH2 CH2 CH2

Negative carbon, a Additional resonance Protonation to

carbanion, basic, form, stabilizing yield enol form.
nucleophilic anion, reducing
carbon. basicity and
nucleophilicity.
 Details…
Base strength
Alkoxides will not cause appreciable ionization of simple
carbonyl compounds to enolate.
Strong bases (KH or NaNH2) will cause complete
ionization to enolate.
O O

Double activation (1,3 dicarbonyl compounds)

will be much more acidic.
H H
For some 1,3 dicarbonyl compounds the enol form
may be more stable than the keto form.
 More details…
Nucleophilic carbon
O

nucleophilicity CH2

Some examples:
O O base O O
R-X O O

O :OH- O O
Br-Br
CH3 CH2 CH2Br
 Some reactions related to acidity of
 hydrogens
Racemization

Exchange
Oxidation: Aldehyde  Carboxylic
Recall from the discussion of alcohols.

Milder oxidizing reagents can also be used

Ag(NH3)2+
RCHO RCO2- + Ag

Tollens Reagent test for

aldehydes
“Drastic Oxidation” of Ketones

CO2H
dichromate, etc
HO2C

at high temperature
O

CO2H

HO2C

Obtain four different products in this case.

Reductions: two electron
OH
O
NaBH4
H

Or LiAlH4

OH
O H2/Pt
H
 Reductions: Four Electron
acid Clemmenson
H H
O
Zn(Hg), HCl

base Wolf-Kishner
H H
O
H2N-NH2

KOH, heat
 Mechanism of Wolf-Kishner, C=O  CH2

H
Recall reaction of primary
amine and carbonyl to give N H These hydrogens
Schiff base. Here is the
O
H2N-NH2 N are weakly acidic,
formation of the Schiff base. just as the
We expect this to happen. hydrogens  to a
carbonyl are acidic.
Weakly acidic H -
OH H
hydrogen removed. N H N H N H
N
Resonance occurs. N
C
C N

Same as keto/enol
tautomerism. O
Here is the resonance for the anion from the keto-enol system
N H N H
N H-O-H
Protonation (like N
C
C H C H
C
forming the enol) H

O O

Perform an -
OH
N H
elimination reaction N
N N
H-O-H H
N N H
to form N2. H
H H
 Haloform Reaction, overall
O
CX3
O CH3
CO2-
X2
NaOH

+ HCX3
NaOH

The last step which produces the

O haloform, HCX3 only occurs if there is
CH3
an  methyl group, a methyl directly
attached to the carbonyl.
 methyl If done with iodine then the formation of
iodoform, HCI3, a bright yellow
precipitate, is a test for an  methyl
group (iodoform test).
 Steps of Haloform Reaction O CX3
O CH3
The first reaction:
X2

NaOH

O CH2X
O CH3

l three H’s replaced by X2

. This must happen
epwise, like this: NaOH

Pause for a sec: We have had three mechanistic discussions of how elemental
halogen, X2, reacts with a hydrocarbon to yield a new C-X bond. Do you recall them?

Radical Reaction: R. + X-X  R-X + X. (initiation required)

Br
Addition to double bond: C=C + X-X  + Br- (alkene acts as nucleophile, ions)
O :OH- O O
Br-Br
Nucleophilic enolate anion: CH3 CH2 CH2Br
 Mechanism of Haloform Reaction-1
Using the last of the three possibilities
O :OH- O O Br-
Br-Br One H has been
C H3 C H2 CH2Br replaced by halogen.
R R R

Repeat twice again to yield C Br3

Where are we? The halogens have been introduced. First reaction completed.

But now we need a substitution reaction. We have to replace the CBr3 group with
OH.
 Mechanism of Haloform - 2
This is a
O
O CH3 X2
CX 3
O substitution
NaOH O-
step; OH-
+ HCX 3
R NaOH R
R
replaces the CX3
and then ionizes
Here’s how: to become the
Attack of hydroxide O
carboxylate
CX3 O
nucleophile. Formation of -
OH
CX3 anion.
tetrahedral intermediate. R
OH

Anticipate the attack… R

Reform the carbonyl double O

CX3 O
OH
O
O-
bond. CX3- is ejected. The OH
halogens stabilize the R R
+ -:CX3 R
+ HCX3
negative carbon.

Neutralization.
 Cannizaro Reaction
conc. KOH
Overall:
2 RCHO RCO2- + RCH2OH
heat

Restriction: no  hydrogens in the aldehydes.

CHO CHO
O H

H3C

 hydrogens No hydrogens

Why the restriction? The  hydrogens are acidic leading to ionization.

 Mechanism
What can happen? Reactants are the aldehyde and concentrated hydroxide.
Hydroxide ion can act both as
Base, but remember we have no acidic hydrogens (no  hydrogens).
Nucleophile, attacking carbonyl group.

O
O O O
R
+ H
R + R
R H R H R O
R H OH
- OH OH
HO : H
H O
Attack of H O
nucleophilic Re-establish C=O and Acid-base
HO- eject H- which is
immediately received
by second RCHO
Experimental Evidence
KOH, H2O
2 RCDO RD2OH + RCO2-

These are the hydrogens introduced by the

reaction. They originate in the aldeyde and do
not come from the aqueous hydroxide solution.
Kinetic vs Thermodynamic Contol of a
Reaction
Examine Addition of HBr to 1,3 butadiene

H
H
HBr
+

Br
Br

1,2 product 1,4 product

 Mechanism of reaction.

Allylic resonance
H
H

H-Br

Br Br
H
H

Br
Br
1,2 product 1,4 product

But which is the dominant product?

Nature of the product mixture depends on the temperature.

H
H
HBr
+

Br
Br

1,2 product 1,4 product

Product mixture at -80 deg 80% 20%

Product mixture at + 40 deg 20% 80%

Goal of discussion: how can temperature control the product mixture?

 When two or more products may be formed in a reaction A  X or A  B

Thermodynamic Control: Most stable product dominates

Kinetic Control: Product formed fastest dominates

Thermodynamic control assumes the establishing of equilibrium conditions

and the most stable product dominates.

Kinetic Control assumes that equilibrium is not established. Once product is

made it no longer changes.

Equilibrium is more rapidly established at high temperature. Thermodynamic

control should prevail at high temperature where equilibrium is established.
Kinetic Control may prevail at low temperature where reverse reactions are
very slow.
Nature of the product mixture depends on the temperature.

H
H
HBr
+

Br
Br

1,2 product 1,4 product

Product mixture at -80 deg 80% 20%

Product mixture at + 40 deg 20% 80%

More stable
Thermodynamic Control product
Kinetic Control

Product formed most

quickly, lowest Ea
Formation of the allylic carbocation.

Can react to yield 1,2 product or 1,4 product.

Most of the carbocation reacts to give the 1,2 product because of the
smaller Ea leading to the 1,2 product. This is true at all temperatures.
At low temperatures the reverse reactions do not occur and the product
mixture is determined by the rates of forward reactions. No
equilibrium.
Most of the carbocation reacts to give the 1,2 product because of the
smaller Ea leading to the 1,2 product. This is true at all temperatures.
At higher temperatures the reverse reactions occur leading from the
1,2 or 1,4 product to the carbocation. Note that the 1,2 product is more
easily converted back to the carbocation than is the 1,4. Now the 1,4
product is dominant.
 Diels Alder Reaction/Symmetry Controlled Reactions

Quick Review of formation of chemical bond.

HO- + H+ H-O-H
Electro Electron
n donor acceptor

HO- + H+ H-O H

Note the overlap of the hybrid (donor) and the s orbital which allows bond formation.

For this arrangement there is no overlap. No donation of

electrons; no bond formation.
Diels Alder Reaction of new bonds
butadiene and ethylene to
yield cyclohexene.

A B
We will analyze in terms of the pi electrons of the two systems interacting. The pi
electrons from the highest occupied pi orbital of one molecule will donate into an lowest
energy pi empty of the other. Works in both directions: A donates into B, B donates into
A. B HOMO donates into A
LUMO
Note the
LUMO overlap
acceptor leading to
bond
LUMO formation
acceptor
A HOMO donates into B
HOMO HOMOLUMO
Note the
donor donor
overlap
B leading to
bond
A formation
 Try it in another reaction: ethylene + ethylene  cyclobutane
new bonds

A B

LUMO
LUM
O
Equal bonding and antibonding
interaction, no overlap, no bond
HOMO formation, no reaction
HOMO

A B
 Reaction Problem

Br excess sodium methoxide

Br
 Synthesis problem

OEt

using only compounds

having two carbons as
HO the source of all carbons in
the target molecule
 Mechanism Problem

Give the mechanism for the following reaction. Show all

important resonance structures. Use curved arrow notation.
O
OH
aq. acid
+ EtOH
heat
OEt