Chapter 7: Alkenes: Reactions and Synthesis

H C C alcohol OH H C C alkane H

X C C

OH

HO C C C C alkene

OH

halohydrin

1,2-diol

X C C

C O carbonyl

1,2-dihalide H C C halide X C C C halide

Addition

X C C alkene + X Y C C

Elimination

Electrophilic Addition
H + H HBr H H H ether Br

Dehydrohalogenation: loss of HX from an alkyl halide to form an alkene

H Br + H H KOH EtOH (ethanol) H + KBr H + H2O

Hydration: addition of water (H-OH) across a double bond to give an alcohol

H + H H2O H H H H+ OH

Dehydration: Loss of water (H-OH) from an alcohol to give an alkene

H OH H H+ H + H2O H H

Addition of Halogens (X2) to Alkenes: 1,2-dihalides

X2 C C alkene X C C 1,2-dihalide X

Br + Br2 Br +

Br Br not observed

1,2-dibromide has the anti stereochemistry Bromonium ion intermediate controls the stereochemistry

Halohydrin Formation
"X-OH" C C alkene X C C halohydrin OH

Br2, H2O

X + HBr OH anti stereochemistry

Organic molecules are sparingly soluble in water as solvent. The reaction is often done in a mix of organic solvent and water using N-bromosuccinimide (NBS) as the electrophilic bromine source.
O + N Br O DMSO, H2O OH Br + O N H O

Note that the aryl ring does not react!!!

For unsymmterical alkenes, halohydrin formation is Markovnikov-like in that the orientation of the addition of X-OH can be predicted by considering carbocation stability
d+ d+
H2O adds in the second step and adds to the carbon that has the most d+ charge and ends up on the more substituted end of the double bond
CH3 Br2, H2O HO CH3 Br
CH3 Br d+

more d+ charge on the more substituted carbon

Br adds to the double bond first (formation of bromonium ion) and is on the least substituted end of the double bond

Hydration of Alkenes: addition of water (H-OH) across the p-bond of an alkene to give an alcohol. 1. Acid catalyzed hydration- Markovnikov addition of H-OH Not a good method for hydration of an alkene 2. Oxymercuration- Markovnikov addition H-OH
CH3 1) Hg(OAc)2, H2O 2) NaBH4 HO CH3 H

3. Hydroboration- Anti-Markovnikov addition of H-OH, Syn addition of H-OH

CH3 1) B2H6, THF 2) H2O2, NaOH, H2O H CH3 H

HO

H B H

H B H B2H6 (diborane)

H H

O tetrahydrofuran (THF)

_ H3B O + borane-THF complex

Reaction of Alkenes with Carbenes to give Cyclopropanes Carbene: highly reactive, 6-electron species.

(sp2-hybridized)

Generation and Reaction of Carbenes: CHCl3 + KOH Cl2C:

dichlorocarbene
CHCl3, KOH H Cl Cl H

+ H2O

+ KCl

Simmons-Smith Reaction (cyclopropanation)

ether

CH2I2

Zn(Cu)

I-CH2-Zn-I = H2C:
methylene carbene
CH2I2, Zn(Cu) ether H H

The cyclopropanation reaction of an alkene with a carbene takes place in a single step. There is NO intermediate. As such, the geometry of the alkene is preserved in the product. Groups that are trans on the alkene will end up trans on the cyclopropane product. Groups that are cis on the alkene will end up cis on the cyclopropane product.
H R H R CH2I2, Zn(Cu) ether

H R

H R

cis-alkene

cis-cyclopropane

H R

R H

CH2I2, Zn(Cu) ether

H R

R H

trans-alkene

trans-cyclopropane

Hydrogenation: Addition of H2 across the p-bond of an alkene to give an alkane. This is a reduction.
H2, PtO2 ethanol

The reaction uses H2 and a precious metal catalyst. The catalysts is not soluble in the reaction media, thus this process is referred to as a heterogenous catalysis. The catalyst assists in breaking the p-bond of the alkene and the H-H s-bond. The reaction takes places on the surface of the catalyst. Thus, the rate of the reaction is proportional to the surface area of the catalyst. To increase the surface area of the catalyst it is finely dispersed on an inert support such as charcoal (carbon, C) Carbon-carbon p-bond of alkenes and alkynes can be reduced to the corresponding saturated C-C bond. Other p-bond bond such as C=O (carbonyl) and CN are not easily reduced by catalytic hydrogenation. The C=C bonds of aryl rings are not easily reduced.

Catalysts: Pt2O (Adams catalyst) or Pd/C mechanism:

The addition of H2 across the p-bond is syn

O H2, PtO2 ethanol O C5H11 Linoleic Acid (unsaturated fatty acid) O OCH3 H2, Pd/C ethanol OH H2, Pd/C

CH3(CH2)16CO2H Steric Acid (saturated fatty acid) O OCH3

H2, Pd/C N ethanol H H2, PtO2 ethanol H

CH3 CH3

CH3 CH3

CH3 H CH3

syn addition of H2

Not observed

Oxidation of Alkenes to 1,2-Diols and Carbonyl Hydroxylation: formal addition of HO-OH across the p-bond of an alkene to give a 1,2-diol. This is an overall oxidation.
1) OsO4 2) NaHSO3 H OH OH

syn addition

H O O Os O O H

osmate ester intermediate - not usually isolate - NaHSO3 breaks down the osmate ester to the product

Ozonolysis: oxidative cleavage of an alkene to carbonyl compounds. The p- and s-bonds of the alkene are broken and replaced with C=O doubled bonds. C=C of aryl rings, CN and C=O do not react with ozone, CC react very slowly with ozone Ozone (O3):
R1 R2 R3 R4 O3, CH2Cl2 -78 C R1 R2 O O O R3 R4

3 O2

electrical discharge

2 O3
O O O ozonide Zn

+ O

R1 R2

R3 R4

R1 O R2 + ZnO + O

R3 R4

molozonide

1) O3 2) Zn O

1) O3 2) Zn O

+ O= C H2

1) O3 2) Zn H

Oxidative Cleavage of 1,2-Diols to Carbonyl Compounds

HO R1 R2 OH R3 R4 NaIO4 THF, H2O
OH O I O O R2 R3 R4

R1 O R2 + ZnO + O

R3 R4

R1

periodate intermediate

OH OH

NaIO4 H

O H O