Organic Chemistry

William H. Brown William H. Brown Christopher S. Foote Christopher S. Foote Brent L. Iverson Brent L. Iverson
6-1

Reactions of Alkenes
Chapter 6

6-2

Characteristic Reactions
Reaction

DescriptiveName(s)
+

C C

HCl (HX) H2O

C C

C C

+ Br2

(X2 ) H2 O

H C C Cl (X) H C C OH (X)Br C C Br (X)

Hydrochlorination (hydrohalogenation) Hydration

Bromination (halogenation)

C C

+ Br2

(X2 )

HO Bromo(halo)hydrin C C Br (X) formation

6-3

Characteristic Reactions
C C
+ Hg(OAc) 2

H2 O

HgOAc Oxymercuration C C HO C C H BH2 C C HO OH C C H H Hydroboration

C C

BH3

C C

+ OsO4

Diolformation (oxidation) Hydrogenation (reduction)

C C

H2

6-4

Reaction Mechanisms
x

A reaction mechanism describes how a reaction occurs

which bonds are broken and which new ones are formed the order and relative rates of the various bondbreaking and bond-forming steps if in solution, the role of the solvent if there is a catalyst, the role of a catalyst the position of all atoms and energy of the entire system during the reaction

6-5

Gibbs Free Energy

x

Gibbs free energy change, G0: a thermodynamic function relating enthalpy, entropy, and temperature
G0 =H0 TS0
exergonic reaction: a reaction in which the Gibbs free energy of the products is lower than that of the reactants; the position of equilibrium for an exergonic reaction favors products endergonic reaction: a reaction in which the Gibbs free energy of the products is higher than that of the reactants; the position of equilibrium for an endergonic reaction favors starting materials
6-6

Gibbs Free Energy

a change in Gibbs free energy is directly related to chemical equilibrium 0 G =RTlnKeq summary of the relationships between G0, H0, S0, and the position of chemical equilibrium
S0<0 H 0>0 G 0>0;the positionofequilibrium favorsreactants S 0>0 Athighertemperatures whenTS 0>H0and G 0<0,thepositionof equilibriumfavors products G 0<0;the positionofequilibrium favorsproducts

H 0<0

Atlowertemperatures whenTS0<H0and G 0<0,thepositionof equilibriumfavors products

6-7

Energy Diagrams
x

Enthalpy change, 0 : the difference in total bond energy between reactants and products
a measure of bond making (exothermic) and bond breaking (endothermic)

Heat of reaction, 0 : the difference in enthalpy between reactants and products

exothermic reaction: a reaction in which the enthalpy of the products is lower than that of the reactants; a reaction in which heat is released endothermic reaction: a reaction in which the enthalpy reaction of the products is higher than that of the reactants; a reaction in which heat is absorbed
6-8

Energy Diagrams
x

Energy diagram: a graph showing the changes in energy that occur during a chemical reaction Reaction coordinate: a measure in the change in positions of atoms during a reaction

Energy Reaction coordinate

6-9

Activation Energy
x

Transition state:
an unstable species of maximum energy formed during the course of a reaction a maximum on an energy diagram

Activation Energy, G: the difference in Gibbs free energy between reactants and a transition state
if G is large, few collisions occur with sufficient energy to reach the transition state; reaction is slow if G is small, many collisions occur with sufficient energy to reach the transition state; reaction is fast
6-10

Energy Diagram
a one-step reaction with no intermediate

6-11

Energy Diagram
x

A two-step reaction with one intermediate

6-12

Developing a Reaction Mechanism

x

How it is done
design experiments to reveal details of a particular chemical reaction propose a set or sets of steps that might account for the overall transformation a mechanism becomes established when it is shown to be consistent with every test that can be devised this does mean that the mechanism is correct, only that it is the best explanation we are able to devise

6-13

Why Mechanisms?
they are the framework within which to organize descriptive chemistry they provide an intellectual satisfaction derived from constructing models that accurately reflect the behavior of chemical systems they are tools with which to search for new information and new understanding

6-14

Electrophilic Additions
hydrohalogenation using HCl, HBr, HI hydration using H2O in the presence of H2SO4 halogenation using Cl2, Br2 halohydrination using HOCl, HOBr oxymercuration using Hg(OAc)2, H2O followed by reduction

6-15

Addition of HX
x

Carried out with pure reagents or in a polar solvent such as acetic acid
Br H H Br CH3 CH=CH2 Propene + HBr CH3 CH-CH2 + CH3 CH-CH2 2Bromopropane 1Bromopropane (notobserved)

Addition is regioselective

regioselective reaction: an addition or substitution reaction in which one of two or more possible products is formed in preference to all others that might be formed Markovnikovs rule: in the addition of HX, H2O, or ROH to an alkene, H adds to the carbon of the double bond having the greater number of hydrogens
6-16

HBr + 2-Butene
x

A two-step mechanism
Step 1: proton transfer from HBr to the alkene gives a carbocation intermediate slow,rate H + determining CH3 CH=CHCH3 + H Br CH3 CH-CHCH3 + Br secButylcation (a2carbocation intermediate) Step 2: reaction of the sec-butyl cation (an electrophile) with bromide ion (a nucleophile) completes the reaction + CH3CHCH2 CH3 Br Bromideion secButylcation (anucleophile) (anelectrophile) fast Br CH3CHCH2 CH3 2Bromobutane

6-17

HBr + 2-Butene
x

An energy diagram for the two-step addition of HBr to 2-butene

the reaction is exergonic

6-18

Carbocations
x

Carbocation: a species in which a carbon atom has only six electrons in its valence shell and bears positive charge Carbocations are classified as 1 , 2 , or 3 depending on the number of carbons bonded to the carbon bearing the positive charge electrophiles; that is, they are electron-loving Lewis acids

6-19

Carbocations
bond angles about a positively charged carbon are approximately 120 carbon uses sp2 hybrid orbitals to form sigma bonds to the three attached groups the unhybridized 2p orbital lies perpendicular to the sigma bond framework and contains no electrons

6-20

Carbocation Stability
a 3 carbocation is more stable than a 2 carbocation, and requires a lower activation energy for its formation a 2 carbocation is, in turn, more stable than a 1 carbocation, methyl and 1 carbocations are so unstable that they are never observed in solution

6-21

Carbocation Stability
relative stability
H H C+ H Methyl cation (methyl) CH3 H C+ CH3 CH3 C+ H Isopropyl cation (2) CH3 CH3 C+

H Ethyl cation (1)

CH3 tertButyl cation (3)

Increasingcarbocationstability

methyl and primary carbocations are so unstable that they are never observed in solution

6-22

Carbocation Stability
we can account for the relative stability of carbocations if we assume that alkyl groups bonded to the positively charged carbon are electron releasing and thereby delocalize the positive charge of the cation we account for this electron-releasing ability of alkyl groups by (1) the inductive effect, and (2) hyperconjugation

6-23

The Inductive Effect

the positively charged carbon polarizes electrons of adjacent sigma bonds toward it the positive charge on the cation is thus localized over nearby atoms the larger the volume over which the positive charge is delocalized, the greater the stability of the cation

6-24

Hyperconjugation
involves partial overlap of the -bonding orbital of an adjacent C-H or C-C bond with the vacant 2p orbital of the cationic carbon the result is delocalization of the positive charge

6-25

Addition of H2O
addition of water is called hydration acid-catalyzed hydration of an alkene is regioselective; hydrogen adds preferentially to the less substituted carbon of the double bond HOH adds in accordance with Markovnikovs rule
CH3CH=CH2 + H2O Propene
CH3 CH3C=CH2 + H2O 2Methylpropene

H2SO4

OH H CH3CH-CH2 2Propanol

H2SO4

CH3 CH3C-CH2 HO H 2Methyl2propanol

6-26

Addition of H2O
Step 1: proton transfer from H3O+ to the alkene
CH3 CH=CH 2
+ +

H O H H

slow, rate determining

CH3 CHCH 3 A 2o carbocation intermediate

Step 2: reaction of the carbocation (an electrophile) with water (a nucleophile) gives an oxonium ion
CH3 CHCH 3
+ +

Step 3: proton transfer to water gives the alcohol

CH3 CHCH3 H H O: O+ H H : : fast CH3 CHCH3 + H O H :OH H : :
+

:O H H

:O-H H

fast

CH3 CHCH 3 H H An oxonium ion O+

6-27

Carbocation Rearrangements
x

In electrophilic addition to alkenes, there is the possibility for rearrangement Rearrangement: a change in connectivity of the atoms in a product compared with the connectivity of the same atoms in the starting material

6-28

Carbocation Rearrangements
in addition of HCl to an alkene
Cl + HCl 3,3Dimethyl 1butene + Cl

2Chloro3,3dimethylbutane 2Chloro2,3dimethylbutane (theexpectedproduct;17%) (themajorproduct;83%)

in acid-catalyzed hydration of an alkene

+ H2 O 3Methyl1butene H2 SO4

OH

2Methyl2butanol

6-29

Carbocation Rearrangements
the driving force is rearrangement of a less stable carbocation to a more stable one
CH3 : : CH3 CCH=CH2 + H H 3Methyl1butene Cl: slow,rate determining CH3 H A2carbocation intermediate
+

CH3 C-CHCH3 + : Cl : :

the less stable 2 carbocation rearranges to a more stable 3 one by 1,2-shift of a hydride ion
CH3 CH 3 C-CHCH3
+

fast

CH3 CH 3 C- CHCH3 H A 3 carbocation 6-30

+

Carbocation Rearrangements
reaction of the more stable carbocation (an electrophile) with chloride ion (a nucleophile) completes the reaction
CH 3 C- CH 2 CH 3 + : Cl : + CH 3

fast

CH 3 CH 3 C- CH 2 CH 3 : Cl :

: :

2-Chloro-2-methylbutane

6-31

Addition of Cl2 and Br2

carried out with either the pure reagents or in an inert solvent such as CH2Cl2
CH3 CH=CHCH3 2Butene
+

Br2

CH2Cl2

Br Br CH3CH-CHCH3 2,3Dibromobutane

addition of bromine or chlorine to a cycloalkene gives a trans-dihalocycloalkane

+

Br2

Br CH2 Cl2 +

Br

Cyclohexene

Br Br trans1,2Dibromocyclohexane (aracemicmixture)

addition occurs with anti stereoselectivity; halogen stereoselectivity atoms add from the opposite face of the double bond we will discuss this selectivity in detail in Section 6.7

6-32

Addition of Cl2 and Br2

Step 1: formation of a bridged bromonium ion intermediate
Br Br C C C Br C C Br C C Br C + Br
-

Thesecarbocationsaremajor contributingstructures

Thebridgedbromonium ionretainsthegeometry

6-33

Addition of Cl2 and Br2

Step 2: attack of halide ion (a nucleophile) from the opposite side of the bromonium ion (an electrophile) opens the three-membered ring to give the product
Br C Br
-

Br C Br Anti(coplanar)orientation ofaddedbromineatoms C C

Br

Br Newmanprojection oftheproduct Br

Br C C Br
-

Br C C Br Anti(coplanar)orientation ofaddedbromineatoms

Br Newmanprojection oftheproduct

6-34

Addition of Cl2 and Br2

for a cyclohexene, anti coplanar addition corresponds to trans diaxial addition the initial trans diaxial conformation is in equilibrium with the more stable trans diequatorial conformation because the bromonium ion can form on either face of the alkene with equal probability, both trans enantiomers are formed as a racemic mixture
Br Br (1S,2S)1,2Dibromo cyclohexane Br

+ Br2

Br Br

Br

Br Br (1R,2R)1,2Dibromo cyclohexane 6-35

Addition of HOCl and HOBr

x

Treatment of an alkene with Br2 or Cl2 in water forms a halohydrin Halohydrin: a compound containing -OH and -X on adjacent carbons
CH3CH=CH2 + Cl2 + H2O Propene HO Cl CH3CH-CH2 + HCl 1Chloro2propanol (achlorohydrin)

6-36

Addition of HOCl and HOBr

reaction is both regiospecific (OH adds to the more substituted carbon) and anti stereoselective both selectivities are illustrated by the addition of HOBr to 1-methylcyclopentene
Br2/ H2O 1Methylcyclopentene OH Br + OH Br + HBr

H H 2Bromo1methylcyclopentanol (aracemicmixture)

to account for the regioselectivity and the anti stereoselectivity, chemists propose the three-step mechanism in the next screen
6-37

Addition of HOCl and HOBr

Step 1: formation of a bridged halonium ion intermediate
: Br : : Br : : H R C C H -Br H
-

Step 2: attack of H2O on the more substituted carbon opens the three-membered ring
: Br: H O: H H R C C H H H : H R : Br : C H C H H
6-38

: Br:

: Br : C C H H R H minorcontributing structure

C C H H R H bridgedbromonium ion

Addition of HOCl and HOBr

Step 3: proton transfer to H2O completes the reaction
H R Br C H C H H
x

H R

Br C C H H
+ H3 O+

+
H

H H

O H

As the elpot map on the next screen shows

the C-X bond to the more substituted carbon is longer than the one to the less substituted carbon because of this difference in bond lengths, the transition state for ring opening can be reached more easily by attack of the nucleophile at the more substituted carbon

6-39

Addition of HOCl and HOBr

bridged bromonium ion from propene

6-40

Oxymercuration/Reduction
x

Oxymercuration followed by reduction results in hydration of a carbon-carbon double bond

oxymercuration
+ Hg(OAc) 2 + H2O 1Pentene Mercury(II) acetate HgOAc Anorganomercury compound OH O + CH3COH Acetic acid

reduction

OH HgOAc

NaBH4

OH H 2Pentanol

O + CH3COH + Hg Aceticacid

6-41

Oxymercuration/Reduction
an important feature of oxymercuration/reduction is that it occurs without rearrangement
1. Hg(OAc)2, H2 O 2. NaBH4 3,3Dimethyl1butene

OH 3,3Dimethyl2butanol

oxymercuration occurs with anti stereoselectivity

Hg(OAc) 2 H H H2O OH H H NaBH4 OH H

HgOAc

Cyclopentene

(Antiadditionof OHandHgOAc)

H H Cyclopentanol

6-42

Oxymercuration/Reduction
Step 1: dissociation of mercury(II) acetate

Step 2: formation of a bridged mercurinium ion intermediate; a two-atom three-center bond

6-43

Oxymercuration/Reduction
Step 3: regioselective attack of H2O (a nucleophile) on the bridged intermediate opens the three-membered ring

Step 4: reduction of the C-HgOAc bond

6-44

Oxymercuration/Reduction
x

Anti stereoselective
we account for the stereoselectivity by formation of the bridged bromonium ion and anti attack of the nucleophile which opens the three-membered ring

Regioselective
of the two carbons of the mercurinium ion intermediate, the more substituted carbon has the greater degree of partial positive character alternatively, computer modeling indicates that the CHg bond to the more substituted carbon of the bridged intermediate is longer than the one to the less substituted carbon therefore, the ring-opening transition state is reached more easily by attack at the more substituted carbon
6-45

Hydroboration/Oxidation
x

Hydroboration: the addition of borane, BH3, to an alkene to form a trialkylborane

H H B H Borane + 3CH2=CH 2 CH 3 CH2 B CH 2 CH3 Triethylborane (a trialkylborane) CH 2 CH3

Borane dimerizes to diborane, B2H6

2BH 3 Borane B 2 H6 D iborane

6-46

Hydroboration/Oxidation
borane forms a stable complex with ethers such as THF the reagent is used most often as a commercially available solution of BH3 in THF
2

:O:

+ B2 H6

+ :O BH3 BH3 THF

Tetrahydrofuran (THF)

6-47

Hydroboration/Oxidation
x

Hydroboration is both
regioselective (boron to the less hindered carbon) and syn stereoselective
+ H CH 3 BH 3 H BR 2 H3C H

1-Methylcyclopentene

(Syn addition of BH 3) (R = 2-methylcyclopentyl)

6-48

Hydroboration/Oxidation
concerted regioselective and syn stereoselective addition of B and H to the carbon-carbon double bond
+ H B H CH3 CH2 CH2 CH=CH2 B CH3 CH2 CH2 CH-CH2

trialkylboranes are rarely isolated oxidation with alkaline hydrogen peroxide gives an alcohol and sodium borate
R3 B + H2 O2 + NaOH Atrialkyl borane 3ROH + Na3 BO3 Analcohol

6-49

Hydroboration/Oxidation
x

Hydrogen peroxide oxidation of a trialkylborane

step 1: hydroperoxide ion (a nucleophile) donates a pair of electrons to boron (an electrophile)
R + RB O-O-H R Atrialkylborane Hydroperoxideion (anelectrophile) (anucleophile) R R B O O H R

step 2: rearrangement of an R group with its pair of bonding electrons to an adjacent oxygen atom
R R B O O H R

+ O-H R B O
R

6-50

Hydroboration/Oxidation
step 3: reaction of the trialkylborane with aqueous NaOH gives the alcohol and sodium borate
(RO)3 B + 3NaOH Atrialkylborate 3ROH + Na3 BO3 Sodiumborate

6-51

Oxidation/Reduction
x

Oxidation: the loss of electrons

alternatively, the loss of H, the gain of O, or both

Reduction: the gain of electrons

alternatively, the gain of H, the loss of O, or both

Recognize using a balanced half-reaction 1. write a half-reaction showing one reactant and its product(s) 2. complete a material balance; use H2O and H+ in acid solution, use H2O and OH- in basic solution 3. complete a charge balance using electrons, e6-52

Oxidation/Reduction
three balanced half-reactions
OH CH3 CH=CH2 + H2 O Propene CH3 CHCH3 2Propanol HO OH CH3 CH=CH2 + 2H2 O Propene CH3 CH=CH2 + 2H+ + 2ePropene CH3 CHCH2 + 2H+ + 2e1,2Propanediol CH3 CH2 CH3 Propane

6-53

Oxidation with OsO4

x

OsO4 oxidizes an alkene to a glycol, a compound glycol with OH groups on adjacent carbons
oxidation is syn stereoselective
OsO4 O O Os O O Acyclicosmate NaHSO3 H2O OH

OH cis1,2Cyclopentanediol (acisglycol)

6-54

Oxidation with OsO4

OsO4 is both expensive and highly toxic it is used in catalytic amounts with another oxidizing agent to reoxidize its reduced forms and, thus, recycle OsO4
HOOH Hydrogen peroxide CH3 CH3 COOH CH3 tertButylhydroperoxide (tBuOOH)

6-55

Oxidation with O3
x

Treatment of an alkene with ozone followed by a weak reducing agent cleaves the C=C and forms two carbonyl groups in its place
CH3 CH3 C=CHCH 2 CH 3 2-Methyl-2-pentene 1. O3 CH3 CCH 3 2. (CH3 ) 2 S Propanone (a ketone) O O + HCCH 2 CH3 Propanal (an aldehyde)

6-56

Oxidation with O3
the initial product is a molozonide which rearranges to an isomeric ozonide
CH 3 CH=CH CH 3 2-Butene O3 O OO CH 3 CH-CHCH 3 A molozonide H H3 C O H O CH 3 CH

C C (CH 3 ) 2 S CH 3 O O Acetaldehyde An ozonide

6-57

Reduction of Alkenes
x

Most alkenes react with H2 in the presence of a transition metal catalyst to give alkanes
+ H2 Cyclohexene Pd 25 C, 3 atm Cyclohexane

commonly used catalysts are Pt, Pd, Ru, and Ni the process is called catalytic reduction or, alternatively, catalytic hydrogenation addition occurs with syn stereoselectivity

6-58

Reduction of Alkenes
x

Mechanism of catalytic hydrogenation

6-59

Reduction of Alkenes
even though addition syn stereoselectivity, some product may appear to result from trans addition
CH3 CH3 1,2Dimethyl cyclohexene H2 / Pt CH3
+

CH3 CH3 30%to15% trans1,2Dimethyl cyclohexane (racemic)

CH3 70%to85% cis1,2Dimethyl cyclohexane

reversal of the reaction after the addition of the first hydrogen gives an isomeric alkene, etc.
CH3 CH3 1,2Dimethyl cyclohexene H2/ Pt H CH3 H Pt HCH3 CH3 CH3 1,6Dimethyl cyclohexene

6-60

 H0 of Hydrogenation
x

Reduction of an alkene to an alkane is exothermic

there is net conversion of one pi bond to one sigma bond

H0 depends on the degree of substitution

the greater the substitution, the lower the value of H

H0 for a trans alkene is lower than that of an isomeric cis alkene

a trans alkene is more stable than a cis alkene

6-61

 H0 of Hydrogenation
Name Ethylene Propene 1Butene cis2Butene trans2Butene 2Methyl2butene 2,3Dimethyl2butene Structural Formula CH2 =CH2 CH3 CH=CH2 H [kJ(kcal)/m ol] 137(32.8) 126(30.1) 127(30.3) 120(28.6) 115(27.6) 113(26.9) 111(26.6)
6-62

Reaction Stereochemistry
x

In several of the reactions presented in this chapter, chiral centers are created Where one or more chiral centers are created, is the product
one enantiomer and, if so, which one? a pair of enantiomers as a racemic mixture? a meso compound? a mixture of stereoisomers?

As we will see, the stereochemistry of the product for some reactions depends on the stereochemistry of the starting material; that is, some reactions are stereospecific
6-63

Reaction Stereochemistry
x

We saw in Section 6.3D that bromine adds to 2butene to give 2,3-dibromobutane

CH3 CH=CHCH3 2Butene
+

Br2

CH2Cl2

Br Br CH3CH-CHCH3 2,3Dibromobutane

two stereoisomers are possible for 2-butene; a pair of cis,trans isomers three stereoisomers are possible for the product; a pair of enantiomers and a meso compound if we start with the cis isomer, what is the stereochemistry of the product? if we start with the trans isomer, what is the stereochemistry of the product?

6-64

Bromination of cis-2-Butene
reaction of cis-2-butene with bromine forms bridged bromonium ions which are meso and identical

6-65

Bromination of cis-2-Butene
attack of bromide ion at carbons 2 and 3 occurs with equal probability to give enantiomeric products as a racemic mixture

6-66

Bromination of trans-2-Butene
reaction with bromine forms bridged bromonium ion intermediates which are enantiomers

6-67

Bromination of trans-2-Butene
attack of bromide ion in either carbon of either enantiomer gives meso-2,3-dibromobutane

6-68

Bromination of 2-Butene
x

Given these results, we say that addition of Br2 or Cl2 to an alkene is stereospecific
bromination of cis-2-butene gives the enantiomers of 2,3-dibromobutane as a racemic mixture bromination of trans-2-butene gives meso-2,3dibromobutane

Stereospecific reaction: a reaction in which the stereochemistry of the product depends on the stereochemistry of the starting material

6-69

Oxidation of 2-Butene
OsO4 oxidation of cis-2-butene gives meso-2,3butanediol H H
H3C C H H3 C C
2 3 2 3

CH3

OsO4 ROOH

HO OH (2S,3R)2,3Butanediol HO OH C
2 3

CH3 cis2Butene (achiral)

identical; ameso compound

H H CH3 H3 C (2R,3S)2,3Butanediol

6-70

Oxidation of 2-Butene
x

OsO4 oxidation of an alkene is stereospecific

oxidation of trans-2-butene gives the enantiomers of 2,3-butanediol as a racemic mixture (optically inactive)
H3 C H C H C
2 3 2 3

CH3 H apairof enantiomers; aracemic mixture

H3 C H trans2Butene (achiral)

CH3

OsO4 ROOH

HO OH (2S,3S)2,3Butanediol HO OH C
2 3

CH3 H H H3 C (2R,3R)2,3Butanediol

and oxidation of cis-2-butene gives meso 2,3-butanediol (also optically inactive)

6-71

Reaction Stereochemistry
x

We have seen two examples in which reaction of achiral starting materials gives chiral products
in each case, the product is formed as a racemic mixture (which is optically inactive) or as a meso compound (which is also optically inactive)

These examples illustrate a very important point about the creation of chiral molecules
optically active (enantiomerically pure) products can never be produced from achiral starting materials and achiral reagents under achiral conditions although the molecules of product may be chiral, the product is always optically inactive (either meso or a pair of enantiomers)
6-72

Reaction Stereochemistry
x

Next let us consider the reaction of a chiral starting material in an achiral environment
the bromination of (R)-4-tert-butylcyclohexene only a single diastereomer is formed
Br2 Br Br redrawas achair conformation Br Br

(R)4tertButyl cyclohexene

(1S,2S,4R)1,2Dibromo4tertbutylcyclohexane

the presence of the bulky tert-butyl group controls the orientation of the two bromine atoms added to the ring
6-73

Reaction Stereochemistry
x

Finally, consider the reaction of an achiral starting material in an chiral environment

BINAP can be resolved into its R and S enantiomers

PPh2 PPh2 BINAP (S)()BINAP []D2 5223 (R)(+)BINAP []D2 5+223

6-74

Reaction Stereochemistry
treating (R)-BINAP with ruthenium(III) chloride forms a complex in which ruthenium is bound in the chiral environment of the larger BINAP molecule this complex is soluble in CH2Cl2 and can be used as a homogeneous hydrogenation catalyst
(R)BINAP + RuCl3 (R)BINAPRu

using (R)-BINAP-Ru as a hydrogenation catalyst, (S)naproxen is formed in greater than 98% ee

CH2 COOH H3 CO + H2 (R)BINAPRu pressure CH3 COOH H3 CO (S)Naproxen (ee>98%)

6-75

Reaction Stereochemistry
BINAP-Ru complexes are somewhat specific for the types of C=C they reduce to be reduced, the double bond must have some kind of a neighboring group that serves a directing group
(S)BINAPRu OH H2 OH

(R)3,7Dimethyl6octen1ol (R)BINAPRu OH

(E)3,7Dimethyl2,6octadien1ol (Geraniol)

(S)3,7Dimethyl6octen1ol

6-76

Reactions of Alkenes
End Chapter 6

6-77