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Chapter 8. Alkenes: Reactions and Synthesis
8.1 Preparing Alkenes: A preview of Elimination Reactions
Addition and elimination reactions are opposite processes.
Alkenes are commonly made by:
• elimination of HX (dehydrohalogenation)
• elimination of H-OH (dehydration)
Recall from Chapter 7 when we looked at an alkyl halide and predicted possible alkenes that could have
made that product?
The same answers result from an elimination reaction:
.
CHEM 257 Fall 2024 Dr. A. Schaefer
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Practice Question:
Give the Elimination Product:
8.2 Halogenation of Alkenes: Addition of X2
• Addition of Br2 and Cl2 gives 1,2-dihaldes
– F2, I2 do not add
– Mechanism is different from addition of H-X
• Addition of X2 is exclusively trans
• Electrophilic addition of bromine is followed by cyclization to give a bromonium ion
– Overall: Br+ adds giving a cyclic ion
–
• The bromoniun ion is an electrophile, Br- is a nucleophile
• Face selectivity
– Br is big, blocks one face of ring
– Reaction yields trans- addition product
– Anti- addition
Show stereochemistry of product formed (types of bonds).
CHEM 257 Fall 2024 Dr. A. Schaefer
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8.3 Halohydrins from Alkenes: Addition of HOX
• Addition of “HO-X” to an alkene
– 1,2-halo alcohol, or halohydrin
• X2 (Br2 or Cl2) in H2O and an organic solvent
Mechanism of Formation of a Bromohydrin
• Br2 forms bromonium ion, then water adds
– Orientation toward stable C+ species
– Anti stereochemistry
Br
Br
Br
Br + Br H2O
H2O
O
H H
An Alternative to Bromine
• Bromine is a difficult reagent to use for this reaction
• N-Bromosuccinimide (NBS) produces bromine
Practice Questions:
Give the products for the following reactions
8.4 Hydration of Alkenes: Addition of H2O by oxymercuration
• Hydration of an alkene
– Addition of “H-OH” to give an alcohol
CHEM 257 Fall 2024 Dr. A. Schaefer
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Acid-Catalyzed Addition of H2O
• Mechanism is similar to addition of H-X
• Water is the nucleophile in second step.
• Deprotonation yields the neutral alcohol
Oxymercuration Intermediates
• For laboratory-scale hydration of an alkene
• Use Hg(OAc)2 in THF then NaBH4
• Markovnikov orientation
– via mercurinium ion (similar to halonium ion)
8.5 Hydration of Alkenes: Hydroboration
• Borane (BH3) is electron deficient (a Lewis acid)
– Adds to an alkene
• Oxidation then yields an alcohol
– Product has non-Markivnakov regiochemistry
• BH3 can add to up to three alkenes trialkylborane
• Treatment with base and H2O2 produces the alcohol
• Regiochemistry is opposite to Markovnikov orientation
CHEM 257 Fall 2024 Dr. A. Schaefer
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– OH adds to carbon with most H atoms
• H and OH add with syn stereochemistry, to the same face of the alkene (opposite of anti addition)
Mechanistic insights of Hydroboration
• BH3: Lewis acid
• Alkene: Lewis base
• BH2–H adds across C=C
• TS involves - B
• No formal C+
• BH2 on more substituted C would create steric strain
• OH adds to less substitued C atom
Practice Questions:
Give the products for the following reactions:
CHEM 257 Fall 2024 Dr. A. Schaefer
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Give the Reagents for the following Transformations
Recognizing Oxidation and Reduction Processes
• In general chemistry:
– “OIL RIG” (What happens to electrons?)
• In organic chemistry:
– What happens to Carbons?
• Reduction:
– Forming:
– Breaking:
• Oxidation:
– Forming:
– Breaking:
8.8 Reduction of Alkenes: Hydrogenation
• Addition of H-H across C=C
• Pt or Pd on carbon (Pd/C) and H2
• Hydrogen is adsorbed on catalyst
• Heterogeneous reaction (not in solution)
CHEM 257 Fall 2024 Dr. A. Schaefer
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Page 7 of 16
Hydrogen Addition-Selectivity
• Selective for C=C of alkenes
– No reaction with C=O, CN, aromatic rings
• Sterics matter: If one side is blocked, H2 adds to the other
Mechanism of Catalytic Hydrogenation
• Heterogeneous – reaction between phases
• Addition of H-H is syn
What is/are the major product(s) produced in the following reaction?
8.7 Oxidation of Alkenes: Epoxidation and Hydroxylation
• Epoxidation results in formation of a cyclic ether
– Three atom ring containing an oxygen (oxirane)
• Addition is syn
• Most common reagent, meta-chloroperoxybenzoic acid (mCPBA)
Mechanism for Epoxidation
Concerted reaction, no intermediates formed.
CHEM 257 Fall 2024 Dr. A. Schaefer
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Page 8 of 16
Two-Step Epoxidation
1. trans-halohydrin formation
2. Base eliminated H-X
Preparation of Diols from Epoxides:
Epoxides can be opened with acid
• Protonation of the epoxide O atom
• Nucleophilic addition of water (:OH2)
– Trans-1,2 diol results
• Similar to opening of bromonium ion.
Osmium Tetroxide Catalyzed Formation of Diols
• Dihydroxylation - converts alkene to syn-diol
• Osmium tetroxide: oxidizing agent (very toxic)
• Reaction occurs via a cyclic osmate diester
• Alternate route: OsO4, acetone and NMO
– NMO = N-Methylmorpholine
– Know this one!
CHEM 257 Fall 2024 Dr. A. Schaefer
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Page 9 of 16
Practice Questions:
Give the reagents for the formation of the following diols
8.8 Oxidation of Alkenes: Cleavage to Carbonyl Compounds
Ozone
• O3, adds to alkenes (molozonide), then rearranges (ozonide)
• Reduction of ozonide yields ketones and/or aldehydes
– Whatever was on alkene carbons stays there
Permangante Oxidation of Alkenes
Potassium permanganate (KMnO4), is stronger than O3
– If H is on alkene carbons:
• Carboxylic acids (1 H on C=C)
• CO2 (2 H on C=C)
CHEM 257 Fall 2024 Dr. A. Schaefer
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Cleavage of 1,2-diols
• Periodic acid, HIO4, cleaves a 1,2-diol into two carbonyl compounds
• Dihydroxylation (OsO4) then diol cleavage (HIO4) is an alternative to ozonolysis
Practice Questions:
Give the products for the following reactions
Give the alkene that yields the following product upon ozonolysis
CHEM 257 Fall 2024 Dr. A. Schaefer
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8.9 Addition of Carbenes to Alkenes: Cyclopropane synthesis
• A carbene is “half of an alkene”
• Divalent carbon, 1 lone pair, 6 e-
– sp2 hybridized, similar to a C+ in geometry
• Add across double bonds to form cyclopropanes
Formation of Dichlorocarbene
• Base removes proton from chloroform
• Stabilized carbanion remains
• Elimination of Cl- gives dichlorocarbene
Addition of dichlorocarbene is stereospecific cis
Simmons-Smith Reaction
• Addition of CH2:
• CH2I2 + zinc-copper alloy produces a “carbenoid” (carbene-metal complex)
Gives cyclopropanes by cycloaddition
CHEM 257 Fall 2024 Dr. A. Schaefer
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8.10 Radical Additions to Alkenes: Chain-Growth Polymers
• Polymers are large molecule with repeating units of simpler molecules
• Alkenes can polymerize by radical addition reactions
• Polyethylene is a polymer of ethylene
Free Radical Polymerization: Initiation
• Initiation - a few radicals are generated
• A bond is broken homolytically
• Propogation:
• Radical adds to alkene to generate alkene derived radical
• This radical adds to another alkene, and the process repeats
• Termination:
• Propagation ends when two radical chains combine
• Hard to control, reaction conditions (concentration, reactivity) affect size of polymer obtained
Practice Questions
Show the monomer units used to prepare the following polymers:
CHEM 257 Fall 2024 Dr. A. Schaefer
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How will the next exam test over Reactions?
• Give the product
• Give the reagent
• Give the reactant
• Give the mechanism
8.12 Reaction Stereochemistry:
• Many reactions form chirality centers
– Racemic product from planar carbocation.
• What is the stereochemistry of the chiral product?
• What relative amounts of stereoisomers form?
It depends on what you start with.
H H
O
H H2O H2O
O OH
H H
• Addition of nucleophile to carbocation (sp 2, planar)
• Top and bottom faces are equally accessible
• Product is a racemate (±)
CHEM 257 Fall 2024 Dr. A. Schaefer
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• Optical activity cannot arise from nothing.
• Must have a chiral reactant, reagent or environment to create optical activity.
Chrial Environment:
• Enzymes
8.13 Reaction Stereochemistry: Addition of H2O to a Chiral Alkene
• Add H2O to a chiral alkene
• Product has 2 chiral centers
For a C+ with a chiral center:
• A chiral center on a intermediate can influence the stereochemistry of the product
– Top and bottom faces are not equal
• Sterics
• Chiral reactant + achiral reagent unequal amounts of diastereomeric product
CHEM 257 Fall 2024 Dr. A. Schaefer
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Chapter 8 Summary
• Alkenes - generated by elimination reactions (loss of H-X, H-OH)
• H-X adds to alkenes in a two-step electrophilic addition process, forming a C + intermediate
• Br2, Cl2 add with a different mechanism, forming a “halonium” ion intermediate, product has anti-
stereochemistry
• If reactants are halogen and water, “X-OH” adds
• Hydration, addition of “H-OH” across a double bond
– Oxymercuration (Hg(OAc)2 then NaBH4) – Markivnakov product
– Hydroboration, oxidation (BH3 then –OH, H2O2) – non-Markivnakov product
• Carbenes (R2C:) neutral molecules, divalent C with 6 valence e-
– Add to alkenes to yield cyclopropanes
– Cl2C:
• Alkenes are reduced
– Addition of H2 + metal catalyst (syn addition of H2)
• Alkenes are oxidized
– Addition of peroxyacids to give epoxides
– Addition of two (-OH) groups (OsO4)
– Cleavage with ozone and KMnO4
• Polymers are large molecules resulting from repetitive bonding of small monomer units
• Typically are formed by radical reactions
• With substituted alkenes, form more highly substituted radical
• Chiral products
• Achiral reagents – racemic mixtures
• Optically active reagents – optically active products
CHEM 257 Fall 2024 Dr. A. Schaefer
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Test your Understanding:
Fill in reagents for the following transformations on alkenes:
Indicate stereo- and regio- chemistry where applicable.
CHEM 257 Fall 2024 Dr. A. Schaefer
FOR STUDENT USE ONLY!
USE BY OR SUBMISSION TO TUTORS OR TUTORING COMPANIES IS PROHIBITED.