Chapter 12: Reactions of Alkenes

Polyethylene

Tear resistant

Addition Reactions of Alkenes

Bond is unsaturated. Reacts by addition. C C + A B C C A B
exothermic (usually)

We can calculate H from bond strength data, using DH-bond = 65 kcal/mol. Note, however: S is negative (~ -30 e.u.)

1. Catalytic Hydrogenation: H2 + catalyst C C + H H

H2

cat.

C C H H

Heterogeneous catalysts

Pd/C, PtO2 (

Pt)

Why catalysts? Enable a lower Ea mechanism. Alkenes + H2 no reaction without catalyst

E
Catalyzed pathway

Uncatalyzed pathway

Mechanism of hydrogenation: Occurs on surface of catalyst. Involves stereospecific HH addition from the same side (syn) of double bond. cat. H CH3 CH2CH3

+ H2
D2

cis

H D
R R

trans

cat.

+ SS

Orbison Lipshutz

Vegetable Oils, Soft Margarine, and Butter: Hydrogenation Hardens

Margarine comes from oleomargarine, in turn derived from : a. Olefins, the original name for alkenes, because addition reactions of many gaseous alkenes give oils as products (from oleum facere, Latin, to make oil); b. margaric acid, one of the constituent fatty acids of margarine, heptadecanoic acid (forms shiny, pearly crystals, Greek, margaron, pearl) The fat molecules in butter and hard (stick) margarines are highly saturated, whereas those in vegetable oils have a high proportion of cis-alkene functions (more than 90%). Partial hydrogenation of these oils yields soft (tub) margarine. Conditions of hydrogenation also isomerize cis double bonds to trans. For example, hard margarine: 35% saturated fatty acids (SFAs), 12% trans fatty acids (TFAs); natural butter >50% SFAs, 34% TFAs. Soft margarine (less hydrgoenation) ~15% SFAs, ~5% TFAs.

TFAs and Health

TFAs not metabolized in same way as cis counterparts; TFAs in foods greatly affect lipid metabolism; TFAs accumulate in cell membranes, increase levels of lowdensity lipoproteins (bad cholesterol) in blood while reducing high-density lipoprotein levels (good cholesterol); Increased risk of breast cancer and heart disease. TFAs are present in fried fast foods (french fries) and many baked goods (cakes, cookies, crackers, and pastries). American Heart Association (2005) recommends: <30% of caloric intake from fat; < 10% trans and saturated fats. USDA (1.1.2006) requires all food to list trans fatty acid content.

2. Electrophilic Additions + Bond is e-rich. Polar reagents AB add to it. + + Mechanism for A = H: Reverse of E1! H - H B :B + + C C +H C C C C

a. Hydrohalogenation + HI
0C

+ H

+ H X
I Reverse of H
HBr

elimination

Br

Regioelective: + HCl

Cl

Markovnikovs Rule
H+ (A +) adds to less substituted carbon Why? Makes the more substituted cation
18381904

PropeneHCl

Caruso Lipshutz

b. Markovnikov Hydration + H OH
solvent
H2SO4

+ H2O, H catalyst

CH3 OH H Equilibrium !

Reversible Hydration of 2-Methylpropene:

H+ consumed H+ regenerated

Consequences of Reversibility of E1
Alkene isomerization
H+ H+

Equilibration = Thermodynamic control

Mechanism of Thermodynamic Control

Step 1

Step 2

Reminder:

C C + A B

c. Halogenation A = B = X

C C A B

X X gets polarized during approach to alkene. + Br2

Br Br

Stereospecific : Anti (not syn) C C or C C

Brominations can be titrated

Stereospecific 2-Butene Bromination

Br Br C

Mechanism:
Br + C C

Br

Br C anti C Br

Precomplex

Django Lipshutz

This Is Hot Recent Stuff!!

Bellucci, Lenoir, Herges, J. Am. Chem. Soc. 1995 Lenoir, Chiappe, Chem. Eur. J. 2003

A Chloronium Ion Structure

Kochi, Chem. Commun. 1998

1.92

2.08

Time Out: Alkenes As Nucleophiles/Bases

Base : Nucleophile : General :

Cylic Halonium Ions : Resonance Forms vs. Isomerization Resonance :

Equilibrium :

Halonium ions can be intercepted by other Nu

Br OH Br + OH2

+ Br2 + H2O
Cf. + O H

via Or X2, ROH

Haloethers

Nu

(all anti and Markovnikov)

H3C H3C + Cl+
CH3OH -H+

+ Cl2 + CH3OH

OCH3 Cl

Synthetically useful in oxymercuration-demercuration

d. Oxymercuration-Demercuration A Markovnikov hydration that avoids cations

O 1. Hg(OCCH3)2, H2O 2. NaBH4 O Or 1. Hg(OCCH3)2, 2. ROH: Gives ethers CH3 OH CH3 OR

Goes through radicals

3. Hydroboration-Oxidation
Allows anti-Markovnikov hydration: RCH = CH2 + H2O RCH2CH2OH Key reaction: B H adds to -bonds. Time out: Borane, BH3, exists as dimer to get octet H + H2B BH2; in THF: H3B O H All three B-H bonds react: H H B H C C B Alkylborane 3 C C + H 3

Hydroboration is regioselective: Steric control of B-H addition + BH3

less hindered

BR2

Why is hydroboration useful?

Oxidation of alkylboranes with H2O2, OH gives ROH [+ B(OH)3] + BH3

H2O2 BR2 OH -

OH

Hydroboration is Stereospecific: Syn addition of BH

H 3C H CH3 B H2O2, -OH H3C H

CH3 OH

+ BH3

Negative charge pushes

Look Familiar?
Positive charge pulls

BH3Oxn

Applications
Think retrosynthetically:
H3C C CH3CH2 CH3 I H OH H OH H3C H CH3 Cl

H CH3

C C

CH3CH2

4. Electrophilic Carbene Additions

Carbenes, :CR2, are 6-electron species, the parent of which is methylene, :CH2. They can be thought of being derived by deprotonating carbocations, CH3+ :CH2 + H+.

C
H

Methylene

Carbenes are electron deficient: electrophilic.

a. Methylene from diazomethane CH2N2

Synthesis (as reactive intermediates)

b. Dichlorocarbene from chloroform

c. Simmons-Smith reagent
CH2I2 + Zn-Cu CH2

Carbenes pick up the two electrons of alkenes to form cyclopropanes.

a.

Stereospecific !
b.

c. Simmons-Smith Reagent in Cyclopropane Synthesis

H H3C C C CH3 H + CH2I2 Zn Cu, (CH3CH2)2O -Metal iodide CH2 H C H 3C C CH3 H

Cyclopropanes are made by nature

H 3C H 3C

(+)- Chrysanthemic acid COOH (used by the flower against insects); the mother of the H3C CH3 Pyrethroids. US market: 1.5 billion $!!

as drugs:

for fun:
HO

Antifungal

OH

Chiral

Addition of Six-electron Species to the -Bond

H : B:H H:

H : :H C :

H :N: :

:O:

:Br:

X +, , or neutral

Oxidation?

5. Electrophilic Oxidation O - + a. Peroxycarboxylic acids RCO OH O C C + RCO OH O C C O + RCOH

Commonly used peroxycarboxylic acids: O O O COOH CH3COOH, CF3COOH,

Peracetic acid Trifluoroperacetic acid

Meta-chloroperbenzoic acid
MCPBA

Cl

+
Cl

O C O OH CHCl3
90%

+
Cl

O COH

Stereospecific: Syn
D H C C H D O + RCOOH
95%

O D H H D

O + RCOH
Aqueous work up

Trans-2,3-dideuteriooxacyclopropane

Mech.:

C C

O H
O

C O
:Nu1

C C

O O + H
H C CH3

C O

Application:

HO C H

1.CH3SO2Cl

H3C H3C H C Nu2 H C CH3

CH3

H3C

Nu1

2. :Nu2

Nu1

Double nucleophilic syn addition to double bond

Rates of oxacyclopropanation increase with alkyl substitution : O + CH3COOH

1 equiv
CHCl3 10C

86%

Sequence 1. RCO3H, 2. H+, H2O or OH, H2O constitutes an anti-dihydroxylation of alkenes. O H3C H RCO3H C C H H3C H CH3 CH3 H H HO CH3 H+, H2O C C or OH, H2O meso H3C OH H

This is at the forefront !

Sarzi-Amad et al. J. Org. Chem. Dec. 2002

Good!

Not good

* -lone pair

stabilization

Non-synchronous concerted

b. Syn-dihydroxylation
Reagents : KMnO4, -OH, or better: OsO4 O O
1. OsO4 2. H2S, H2O

VIII

Os

O O

is reduced to OsVI. OH OH

Cis-1,2-cyclohexanediol

Gives complementary stereochemistry to anti-dihydroxylation

Mech.:

C C

O O

VIII

Os

O O O O

C C

O O

Os

VI

O O

H2O

Six electron TS

C C

OH OH

Osmate ester Os
VI

HO HO

Can be reoxidized by added oxidant, therefore can be made catalytic in Os

Good because Os is expensive; OsO4, H2S are toxic.

O + CH3 N Other oxidants: H2O2 ; Fe3+; and catalytic OsO4 O

c. Ozonolysis
Ozone generator:

Complete oxidative cleavage by 1. O3, 2. Reduction of ozonide 2-4% C

3

O2 C

Arc discharge 1. O3

O O

O+

in O2 C O
90%
H O

2. Reduction

CH3CH2 H3C

C CH3

CH3 1. O H

2. Zn, CH3COOH Zn2+ O

CH3CH2CCH3 + CH3CH

1. O3 2. H2 , Pt H2O

Ring opening

85%

H3C

1. O3 2. (CH3)2S (CH3)2SO

H3C

O
76%

H Clip off carbon atom

Ozonolysis

6. Radical Hydrobromination
Recall: But: + HBr + HBr
RO-OR

Markovnikov Br AntiBr Markovnikov!

Mechanism different; goes via faster, radical chain. Popular peroxides :

Compare to radical halogenation of hydrocarbons:

Does not occur for HCl, HI: One of the propagation steps endothermic, hence too slow, and ionic mechanism of Markovnikov addition wins. But works for RSH, HCX3 anti-Markovnikov additions.

Chloroform Additions
H CH3(CH2)5CH=CH2 + HCCl3 Mechanism: RO Not: + CHCl3
ROOR

CH3(CH2)5CHCH2CCl3
24% 1,1,1-Trichlorononane

ROH +

CCl3

Chain carrier

RO + ClCHCl2
ROOR

ROCl + CHCl2

General: RCH=CH2 + AB RCHCH2B A

For alkene metathesis: Two alkenes exchange their doublebonded carbon atoms,

Chemistry Nobel Prize 2005

Chauvin, Schrock, Grubbs

7. Alkene Polymerization

a. Cationic: C

+ H+
C C R

H C H C N RO B

+ R etc. C C C R H

b. Radical: RO + C c. Anionic: B +
C

- C N C

Resonance

d. Metal (Ti, Zr, lanthanides): Ziegler-Natta; now

Kaminski-Brintzinger. Organometallic mechanism

R Ti

CH3

Insertion

R Ti

CH3

Ti

CH3

a. Acid-catalyzed Polymerization
Proceeds through carbocations (another complication), in addition to SN1, E1, and rearrangements; dominates at high concentrations.

Controlled Oligomerizations in Nature Acid-catalyzed Steroid Synthesis: Stepwise

This one is weird; makes sec. cation. True?

b. Radical Polymerization

Not true stepwise, then concerted :

Corey; Jorgensen; Hess, J. Am. Chem. Soc. 1995; 1997; 2002.

Tert-cation first. Would need rearrangement to secondary: ~10 kcal/mol uphill. Necessary? No!
Last two rings : concerted !
TS

8. Alkenes in Nature: Pheromones

Sex, war, communication (trail, alarm, defence)
NO2 O O O

Termite defence

Black tail deer (hoof excretion); recognition and status

O OH

Queen bee substance, inhibits ovary development in workers, attractsexcites drones Limonene: Bee sting, alarm, aggression

cis-Tetradecenyl acetate: Sex attractant for

the European corn borer

SF Chronicle 2003

Male feeds on an azacyclopentane rich diet, includes this chemical in his sperm, protects female and eggs. Female senses chemicallyrich prospective mating partner!

The Holy Grail: Human Sex Pheromones

C&EN, Feb. 2003