Organic Chemistry
4 th Edition
Paula Yurkanis Bruice
Chapter 4
Reactions of
Alkenes
Irene Lee
Case Western Reserve University
Cleveland, OH
©2004, Prentice Hall

Electrophilic Addition of Alkenes

Addition of Hydrogen Halides

What is the product?

Carbocation formation is the rate-limiting step a more stable carbocation

Carbocation Stabilities

Alkyl groups decrease the concentration of positive charge in the carbocation

Delocalization of Electrons

Molecular Orbital Diagram in a
Hyperconjugation System

Hammond postulate: the transition state will be more similar to the species that it is closer to energetically
Exergonic reaction: early transition state
Endergonic reaction: late transition state

I: early transition state
II: mid-transition state
III: later transition state

Reaction Rate and
D
G
‡ more stable transition state lower
D
G
‡ faster reaction rate

Markovnikov’s Rule
The electrophile adds to the sp 2 carbon that is bonded to the greater number of hydrogens
In a regioselective reaction, one constitutional isomer is the major or the only product

tert -Butyl cation is formed faster and it is more stable

Addition of Water to Alkene

Hydration of Propene

Acid-Catalyzed Addition of Alcohol

Rearrangement of Carbocation
1,2-hydride shift a more stable carbocation

Rearrangement of Carbocation
1,2-methyl shift a more stable carbocation

Carbocation does not always rearrange …

Carbocation Rearrangement
Ring Expansion a more stable carbocation

Addition of Halogens to Alkene

Addition of Halogens in the Presence of Water

Consider the transition states …

Oxymercuration and Mercuration of Alkene

Demercuration by Reduction

Addition of Borane
Hydroboration –Oxidation
AntiMarkovnikov’s rule in product formation

Anti-Markovnikov addition
Markovnikov addition
(a pericyclic reaction)

Formation of Alkyl Boranes

OH Replacement of Boron

Anti-Markovnikov Addition of an OH Group

Reaction of Carbene with Alkene

Synthesis of Bromobutane

Generation of Radicals

Addition of Radicals to Alkene

Relative Stabilities of Alkyl Radicals

Calculating the Change in H
°

Addition of Hydrogen to Alkenes

Catalytic Hydrogenation of an Alkene

Potential Energies of Pentene Isomers

Relative Stabilities of Alkenes

Steric Strain in Alkenes

Relative Stabilities of Dialkyl-
Substituted Alkenes