Chapter 5.1-5.

4
Tuesday May 5th
Don’t get overwhelmed!
• Pay attention to the basic principles of the mechanism
• We still be following the fundamental principles
• What has electrons? (nucleophiles)
• What wants electrons? (electrophiles)
• Remember to identify Lewis acids, Lewis bases and leaving groups
• Carbocations OR partial positive charges will always favor the most substituted side of the
double bond.

• The intermediates will have the most stable carbocation or carbon radical just like we
have always seen

• Addition of the atoms may go in the opposite order

 5.1: General Alkene Reactions
• Substances add across C=C bond
 5.3: Writing Reactions
• Reactants, catalysts written above arrow

• Solvents written below arrow

• Multiple steps are listed sequentially

• Balancing is less important

5.2: Halogenation of Alkenes
• Add Br2 or Cl2 across double bond

• Alkene is nucleophile
• X2 serves as both electrophile and leaving group
 Mechanism
• Does the mechanism involve carbocations?
• If yes, there should be carbocation shifts
Cl
Cl
Cl2

Cl
Cl
ONLY product NOT observed

Cl
Cl

• No carbocation shift = this mechanism is wrong

• Further mechanism testing in Chem 241 experiment 5
Mechanism of Bromination
 Mechanism of Bromination

Step 1: Addition.
 Mechanism of Bromination

Step 2: Bromide attack.

Bromide must attack the carbon from the opposite side

to the bromonium cation. This is why the reaction is an
anti-addition reaction. -Stereoselective
 Mechanism

Advantage over carbocation – every atom has octet

Disadvantage – 3 membered rings are unstable due to angle strain
 Halohydrin Formation

Reaction of bromine with alkenes in the presence of water

yields vicinal halohydrins (halogen and a hydroxyl on
adjacent carbons).
 Modified Halogenation - Halohydrins
• What if another nucleophile intercepts Br- in the final step?
• If water is solvent, it can compete with bromide
 Selectivity of Halohydrins
• Regioselective – alcohol follows Markovnikov’s Rule
• Halonium ion shows some carbocation character
• More substituted C has bigger d+, more electrophilic

 
• More in Chapter 11
Br
 Mechanism of Halohydrin Formation
The regioselectivity arises in the step where water
(the nucleophile) attaches to the bromonium cation:
Halogenation

• Stereoselective Anti addition

• Regioselective for the addition of water (2 Br’s cant tell
regioselectivity)
• No rearrangements suggests no carbocation intermediate
• Halonium ion intermediate
 5.4: Alkene Hydration (Part 2)
• Adding acidic water obeys Markovnikov’s Rule

• Limitations – harsh conditions, cation shifts

• Other methods:
 Oxymercuration
• 2-step method to add water
• Step 1 – Oxymercuration
• Step 2 – Reduction to remove the mercury
 Part 1A – Adding Mercury

• Mechanism – mercurinium ion

• Compare with bromonium ion (5.2)

 Part 1B – Adding Water
• Mercurinium ion reacts with water (or other nucleophiles)

• Compare with halohydrins

• Selectivity is the same for both, water attacks more crowded carbon
(more electrophilic) Regioselective. Anti addition stereoselective
Part 1C – acid-base cleanup
 Part 2 – Reduction
• Hydride is nucleophilic, displaces mercury
• Electron transfer (redox) produces Hg(0)
• Mechanism is complex DON’T NEED TO KNOW IT
 Selectivity
• Alcohol is regioselective for more crowded position
• Due to mercurinium ion intermediate
• No carbocation rearrangements
• No free carbocation intermediate
 Hydroboration of Alkenes
• Adding water to alkenes is regioselective
• What if we want the OTHER isomer?

• This is sometimes called “anti-Markovnikov” as if it breaks the rules

• As in all reactions, the regioselectivity is completely explained by
the mechanism
• Part 1 – add boron to alkene, part 2 – oxidize boron to OH
• OVERALL we have a syn addition stereoselective
 Part 1 – Adding Boron
• Similar to H-OH, H-BH2 adds across the C=C bond

• Borane (BH3) can add 3 times

• Stoichiometry – multiple additions are important

• Mechanism – can pretend borane only adds once
 Selectivity
• Addition is concerted, both H, B are added at same time

• Boron has low electronegativity, is electron-donating group

• Prefers less crowded C to avoid partial carbocation
 Part 2 - Oxidation
• Peroxide supplies O to replace B
• Mechanism is complex
• Key idea – the carbon attached to B is the same
carbon to be attached to OH
First step is deprotonation of H2O2
Step 1: Deprotonation.

Step 2: Nucleophilic attack.

Lewis Acid Still!

 Step 3 rearrangement
Does not need the
• Carbon migration negative charge
• Oxygen adds to the
carbon in the same
location as the Peroxides have weak
boron occupied O-O bonds!
Last step exchange of a hydrogen for a boron

• Regioselective for the Anti-Markovnikovs alcohol

• Stereoselctive SYN addition. The OH and the H add to the same face
of the double bond.
 Comparing Hydration Methods
Method Acidic water Oxymercuration Hydroboration

Regioselectivity More crowded More crowded Less crowded

alcohol alcohol alcohol
Carbocation Yes No No
Shifts?
Nucleophile Alkene Alkene Alkene

Electrophile H+ Hg2+ BH2+

Health Requires strong, Requires toxic Hg Generally okay

considerations corrosive acids compounds