CHAPTER 8—REACTIONS OF ALKENES

8-1 Major products are produced in greatest amount; they are not necessarily the only products produced.
Cl
H
(a) H Cl C Cl

H
I
(b) Cl (c)
Cl C H I
H Cl C H H I

H Br
H
(d) C H Br Produced in about
CH Br
H Br equal amounts;
+ +
each is a mixture
of cis and trans.

Both 2° carbocations will form.

8-2 allylic
H H H H H H
(a)
C
H Br
H H H H H C H
H H
H H H H H H

Br Br

H H H H
Because the allylic carbocation Br
has partial positive charge at two
carbons, the bromide nucleophile
can bond at either electrophilic H H + H H
carbon, giving two products. H H H
H H 3-bromobut- Br H 1-bromobut-2-ene
1-ene
(b)
Cl Cl Cl
Cl Br
C C Br
H Br CH2 CH2

This orientation produces a carbocation

intermediate that is stabilized by
resonance with the Cl atom.
Cl H

CH
This possible intermediate is not produced; it is a 2° carbocation without any stabilization.
201
Copyright © 2017 Pearson Education, Ltd.
 O O O
8-3 ∆
(a) initiation steps H3C C O O C CH3 2 H3C C O radical—no charge
O O

H3C C O H Br H3C C OH Br

propagation steps
Br C The 3° radical is more
Br
stable than the 2° radical.

1-bromo-2-methylcyclopentane
H (cis + trans)
C
Br Br
H Br Br recycles in first
propagation step

(b) initiation steps ∆

O O 2 (CH3)3C O

(CH3)3C O H Br (CH3)3C OH Br
H
propagation steps C Br The benzylic radical is
Br stabilized by resonance, and
Ph Ph
(Recall that "Ph" more stable than the aliphatic
is the abbreviation radical.
for "phenyl".)
H H
C Br Br
Ph Ph recycles in first
H Br H Br propagation step

2-bromo-1-phenylpropane

Br
8-4 HBr
HBr Br
(a) (b)
ROOR
∆
Br
(c) OH
H2SO4 HBr
Note: A good synthesis uses
∆ major products as intermediates,
not minor products. Knowing
OH orientation of addition and
H2SO4 HBr elimination is critical to using
(d) reactions correctly.
∆ ROOR
∆ Br

202
Copyright © 2017 Pearson Education, Ltd.
8-5 CH3 H CH3 H CH3
H methyl
shift CH3
C CH3
CH3 H H O H CH3 C H CH3
CH3 CH3
2° 3°
H H H H
O H
O H
H
H
CH3 CH3
CH3 CH3 CH3
CH3 CH3
CH3 CH3 CH3
HO O H O CH3
H H H
2,3-dimethylbutan-2-ol H H CH3
2,3-dimethylbut-2-ene
+ H3O+ H
OH OH + H3O+
8-6
(a) H (b) (c) In this problem, the H
OH H and OH added in the
hydration reaction are
from 3° benzylic carbocation shown in red.
from 3° carbocation
8-7 OAc
CH3
CH3 H Hg HgOAc
Hg(OAc)
(a) CH3
HOCH2CH3 CH3
CH3 CH3 CH3 H H O
CH3 CH3 H
CH2CH3
mercurinium ion
O
AcO
H3C C
CH3 CH3
"Ac" = acetyl
H HgOAc
(b) CH3 NaBH4 CH3 O
CH3 demercuration CH3
O O H3C C O
H H "OAc" or "AcO" = acetate
CH2CH3 CH2CH3
8-8 CH3
HO Hg(OAc) HO Hg(OAc)
OCH3
(a) (b) (c) Cl Cl
H +
Hg(OAc) OCH3
plus the enantiomer plus the enantiomer of each
Note: When new chiral centers are generated from achiral or racemic reactants, the products are
racemic mixtures. This book will indicate a racemic mixture by adding "plus the enantiomer".
203
Copyright © 2017 Pearson Education, Ltd.
8-8 continued
(d) OCH3
Cl Cl The cis and trans stereoisomers of each positional isomer
would also be produced.
+
OCH3

8-9 OCH3
Hg(OAc)2 NaBH4
(a)
CH3OH
OH
I KOH, ∆ Hg(OAc)2 NaBH4
(b)
Heat favors H2O
elimination.
OH Using an acid-catalyzed hydration in part
Hg(OAc)2 NaBH4 (c) would initially form a 2° carbocation
(c) that would quickly rearrange to 3° on
H2O carbon-3. The desired product would
not be synthesized.
8-10 H
BH3 • THF H2O2
(a), (b) BH2 OH
HO–

BH3 • THF H2O2

(c), (d) racemic mixture
H HO–
BH2 OH

CH3 H CH3 H
BH2 OH
BH3 • THF H2O2
(e), (f) H H
HO– plus the enantiomer

8-11
BH3 • THF H2O2 HO
(a)
HO–
OH
Hg(OAc)2 NaBH4
(b) racemic mixture
H2O

KOH, ∆ BH3 • THF H2O2

(c)
HO– OH
Br
8-12 The attack of borane on 1-methylcyclopentene is equally likely from the top face or the bottom face,
leading to a racemic mixture of the trans isomer.
BH3 • THF BH2 H H2O2 OH H racemic
HO– mixture
H CH3
H CH3 H CH3
204
Copyright © 2017 Pearson Education, Ltd.
8-13 The products are racemic. OH
(a) CH3 CH3 (b) (c) OH
+
OH H H
OH
major minor—steric CH3
racemic hindrance to
mixture BH3 goes on the less
trans product attack of BH3 hindered top (exo) face
plus the enantiomer of the C=C.
R R S S
8-14

Et Et BH3 • THF H2O2 Et Et Et Et

(a) * * * *
Me H HO– Me
H HO H H
Me H OH
Z

enantiomers

R S S R

Et H BH3 • THF H2O2 Et H Et H

(b) * * * *
Me Et HO–
E
Me
H HO Et H
Me Et OH

enantiomers
The enantiomeric pair produced from the Z-alkene is diastereomeric with the other enantiomeric pair
produced from the E-alkene. Hydroboration-oxidation is stereospecific, that is, each alkene gives a specific
set of stereoisomers, not a random mixture.

8-15
Hg(OAc)2 NaBH4
(a)
H2O
OH

BH3 • THF H2O2

(b) plus the enantiomer
HO–
H
OH
H3C OH CH3 CH3
OH
(c) H2SO4 BH3 • THF H2O2
plus the enantiomer
∆ HO–

205
Copyright © 2017 Pearson Education, Ltd.
8-16 (a) top
H Br Br
H H Br
CH3 CH3 CH3
CH3 CH3 CH3
bottom H H3C
empty p orbital in Br
planar carbocation
CH3 Br
The planar carbocation is responsible for non-stereoselectivity. The bromide nucleophile can attack from
the top or bottom, leading to a mixture of stereoisomers. The addition is therefore a mixture of syn and anti
addition.
H
(b) BH3 H HO
2 2 Two methyl groups are
H B H HO always cis to each other.
HO–
CH3 CH3
CH3 CH3 CH3 CH3
In contrast to part (a), hydroboration has no planar intermediate. Borane adds in a molecular addition with
syn stereochemistry, and replacement of B with O proceeds with retention of stereochemistry. All of the
steps in the process are stereospecific, so the product will be one diastereomer (although a racemic mixture).

8-17 During bromine addition to either the cis- or trans-alkene, two new chiral centers are being formed.
Neither alkene (nor bromine) is optically active, so the product cannot be optically active.
The cis-but-2-ene gives two chiral products, a racemic mixture. However, trans-but-2-ene (shown on
the next page), because of its symmetry, gives only one meso product, that can never be chiral. The "optical
inactivity" is built into this symmetric molecule.
This can be seen by following what happens to the configuration of the chiral centers from the
intermediates to products, below. (The key lies in the symmetry of the intermediate and inversion of
configuration when bromide attacks.)
IDENTICAL—SYMMETRIC

CIS
Br CH3 H3C
H H
H H Br2
C C +
CH3 CH3
H H
CH3 H3C Br

Br OR Br A Br– nucleophile could

attack at either carbon.
CH3 CH3

H Br CH3 H Br Br H CH
3 Br H
+
Br H H Br
H H
Br CH3 CH3 Br
CH3 CH3
2S,3S ENANTIOMERS 2R,3R

See the TRANS case on the next page.

206
Copyright © 2017 Pearson Education, Ltd.
8-17 continued ENANTIOMERIC

TRANS
Br CH3 H
H CH3
H CH3 Br2
C C +
CH3 H
H CH3
CH3 H Br
Bromide attack on this
A Br– nucleophile could Br OR Br bromonium ion gives the
attack at either carbon. same results.

CH3 CH3

Br
2
H CH3 H Br Br H3C H
H
3
Br
3 2 2 3
3 + 2
Br H H Br
CH3 H
Br H CH3 Br
CH3 2R,3S 2R,3S CH3
IDENTICAL—MESO

CONCLUSION: Anti addition of a symmetric reagent to a symmetric cis-alkene gives racemic product,
while anti addition to a trans-alkene gives meso product. (We will see shortly that syn addition to a cis-
alkene gives meso product, and syn addition to a trans-alkene gives racemic product. Stay tuned.)
8-18 Enantiomers of chiral products are also produced but not shown.
Br
Br
(a) + Br Br + Br + the enantiomer
Br

(b) Three new asymmetric carbons are produced in this reaction. All stereoisomers will be produced with
the restriction that the two adjacent chlorines on the ring must be trans.
Cl Cl
+ Cl
+ Cl Cl CH3 Cl
CH3

Cl Cl

Cl
CH3 Cl
Cl
Cl CH3
(Hex) Hex
Br Br Hex
(c) H C6H13 H
+ Br Br H Br
C C
C2H5 H Br
E H H Br
(Et) H Hex Et Br
The bromonium ion could form on either face of Et H
Et
the C=C, and bromide will attack the other plus the enantiomer
carbon of the bromonium ion as well. Either
leads to equal amounts of the two enantiomers. 207
Copyright © 2017 Pearson Education, Ltd.
8-18 continued Hex
(d) H Br Br H
H Hex
C C + Br Br Br H
C2H5 C6H13 Br H
Z H H Br
(Et) (Hex) H Et Br
Et Hex
Et
The bromonium ion could form on either face of the plus the enantiomer
C=C, and bromide will attack the other carbon of the
bromonium ion as well. Either leads to equal
amounts of the two enantiomers.
8-19 The trans product results from water attacking the bromonium ion from the face opposite the bromine.
Equal amounts of the two enantiomers result from the equal probability that water will attack either C-1 or C-
2.
Br Br
Br Br H Br H
H2O
H H
H H H O H H OH
plus the enantiomer
H
H2O
Water will do nucleophilic equal amounts of enantiomers =
attack at either carbon. racemic mixture
8-20 enantiomer of product
H
in Solved Problem 8-5
from Solved Problem 8-5 H H H
O OH
The bromonium ion CH3 O H O H
shown here is the CH3 CH3
enantiomer of the one Br
shown in Solved Br Br
Problem 8-5.
H H H
from Solved Problem 8-6: The bromonium ion shown is meso as it has a plane of symmetry; attack by the
nucleophile at the other carbon from what is shown in the text will create the enantiomer.
H H
Cl
Br
Br
H
H Cl These are the enantiomers of
Show products from H H the structures shown in the text.
both nucleophiles Br
attacking at this O H
carbon from the "top" H
face. OH
8-21 The chiral products shown here will be racemic mixtures.
H H
(a) H3C OH (b) (c) H3C Cl (d) H3C Cl
Cl
HO
Br
plus the enantiomer HO H HO CH3
plus the enantiomer CH3 H
plus the enantiomer plus the enantiomer
(e) CH3 OH CH3 Cl
Br Br
+
208
plus the enantiomers Copyright © 2017 Pearson Education, Ltd.
 Cl Cl Cl
OH
8-22 (a) Cl2 OH
(b) KOH Cl2
H2O
∆ H2O
CH3 CH3 plus the
CH3 OH OH enantiomer
H2SO4 Cl2 Cl plus the
(c)
∆ H2O enantiomer

H
8-23 CH3
(a) (b) (c) CH3 (d)
H

8-24 Limonene, C10H16, has three elements of unsaturation. Upon catalytic hydrogenation, the product,
C10H20, has one element of unsaturation. Two elements of unsaturation have been removed by hydrogenation
—these must have been pi bonds, either two double bonds or one triple bond. The one remaining unsaturation
must be a ring. Thus, limonene must have one ring and either two double bonds or one triple bond. (The
structure of limonene is shown in the text in Problem 8-23(d), and the hydrogenation product is shown above
in the solution to 8-23(d).)
8-25 The BINAP ligand is an example of a conformationally Cl
hindered biphenyl as described in text section 5-9A and Figure Ru
5-18. The groups are too large to permit rotation around the Cl
single bond connecting the rings, so the molecules are locked P
into one chiral twist or its mirror image. P

This simplified three-dimensional drawing of one of the

enantiomers shows that the two naphthalene rings are
twisted almost perpendicular to each other. Molecular
models will help visualize this concept.
8-26 Stereochemistry of the starting material is retained in the product. Products are racemic.
cis cis
H H
(a) CH2I2 (b) CH2I2

H Zn, CuCl H H H Zn, CuCl H H

trans trans
OH OH
8-27
(a) Cl (b) H + Probably minor—the OH crowds the
Cl top face of the C=C.
H
H
probably major H
BOTTOM VIEW
(c)
The original 6-membered ring is shown in site of original
bold bonds; arrows point to new bonds. new bonds double bond
Br Br
side view
209
Copyright © 2017 Pearson Education, Ltd.
8-28
(a) CH2I2
Zn, CuCl

CH2Br2 H
(b)
50% NaOH (aq)
Br
Cl
OH Cl
(c) H2SO4 CHCl3
∆ 50% NaOH (aq)

8-29 All chiral products in this problem are racemic mixtures.

H
(a) (b) (c) (d)
O H

O O H
O H
8-30 HA is a generic acid catalyst. It could be RCOOH produced in the epoxidation.

R O O H
(a) C O H A
O H
O
H H H H H H
Et Et Et Et
C C
Et Et
cis H O OR O H
H H
ENANTIOMERS

(H2O removes
Et H OH HO H Et H+ from oxygen.) Et H OH HO H Et
− H+
+ +
H H H H
HO Et Et OH H2O Et Et OH2

(b) R O O H
C O
H A
O H
O
H Et H Et H Et
C C Et H Et H
Et H
trans H O OR O H
H H

mechanism continued on next page

210
Copyright © 2017 Pearson Education, Ltd.
8-30 continued IDENTICAL—MESO from previous page

(H2O removes
Et H OH HO Et H H+ from oxygen.) Et H OH HO Et H
− H+
+ +
Et H Et H
HO H Et OH H2O H Et OH2
stereochemistry shown in Newman projections:
π bond O H OH
OH OH
Et H
H Et rotate
Et H H Et H Et
Et H H2O
H Et H Et
OH
trans (after H2O removes H+ from oxygen)
MESO
Remember the lesson from Problem 8-17: anti addition of a symmetric reagent to a symmetric cis-alkene
gives racemic product, while anti addition to a trans-alkene gives meso product. This fits the definition of
a stereospecific reaction, where different stereoisomers of the starting material (cis and trans) are
converted into different stereoisomers of product (a dl-pair and meso form).
8-31 R
R C O R=
C O
O H
O H O C O Mg2+
O
H O
C C
H
trans H
H

8-32 All chiral products in this problem are racemic mixtures. CH2CH3
(a) (b) CH3CH2H OH HO H Anti addition to a
trans-alkene gives
HO H meso product.
O CH2CH3
HO H
CH2CH3
OH
O
(c) rotate H
CH3 (d) H OH This is the (e) trans
HO cis product. OH
H H
H OH
H
OH
8-33
H Cl − H+
O H O H OH + OH H
(CH3OH removes
H+ from oxygen.)
H H H or H CH3O H H OCH3
CH3 O enantiomers
H
211
Copyright © 2017 Pearson Education, Ltd.
8-34 All these reactions begin with achiral reagents; therefore, all the chiral products are racemic.
CH2CH3
(a) (b) (c) H
OH OH CH3 OH
HO H
OH OH
CH2CH3 HO H
HO H
CH3
H H H
(d) CH3 OH (e) CH3 OH (f) CH3 OH

H H CH2CH3
HO CH2CH3 HO CH2CH3 HO H
same as (d)! same as (c)!
CH2CH3 CH2CH3 CH2CH3

H OH H OH HO H
HO H HO H HO H

CH3 CH3 CH3

Refer to the observation in the solution to Problem 8-35.

8-35

(a) OsO4
meso
H2O2
HO OH
(b) CH3CO3H
racemic (d,l)
H2O
HO OH

(c) CH3CO3H rotate

meso
H2O
HO OH

(d) OsO4 rotate

racemic (d,l)
H2O2
HO OH
Have you noticed yet? For symmetric alkenes and symmetric reagents (addition of two identical X groups):

cis-alkene + syn addition → meso Assume that cis/syn/meso +1 x +1 = +1

cis-alkene + anti addition → racemic are "same", and trans/anti/ +1 x −1 = −1
racemic are "opposite".
trans-alkene + syn addition → racemic Then any combination can −1 x +1 = −1
trans-alkene + anti addition → meso be predicted, just like math! −1 x −1 = +1

212
Copyright © 2017 Pearson Education, Ltd.
8-36 Solve these ozonolysis problems by working backwards, that is, by "reattaching" the two carbons of
the new carbonyl groups into alkenes. Here's a hint. When you cut a circular piece of string, you still have
only one piece. When you cut a linear piece of string, you have two pieces. Same with molecules. If
ozonolysis forms only one product with two carbonyls, the C=C had to have been in a ring. If ozonolysis
gives two molecules, the C=C had to have been in a chain.

(a) Two carbonyls from (b) Two carbonyls from (c) Two carbonyls from ozonolysis
ozonolysis are in a chain, so ozonolysis are in two different are in two different products, so
alkene had to have been in a products, so alkene had to have alkene had to have been in a chain,
ring. been in a chain, not a ring. not a ring.

E or Z of
alkene cannot
be determined
from products.
8-37 H
O3 Me2S O
(a) + O
–78 °C
OH
KMnO4 O
(b) + O
∆

O3 Me2S
(c) O + O
–78 °C

O3 Me2S H
(d)
–78 °C O O

KMnO4 OH
(e)
∆ O O

(f) KMnO4
OH
cold OH groups are cis ; product is racemic.
OH

8-38 The representation for a generic acid is H—A, where A is the conjugate base.
(a) H H H H
H
H A A
C H C
H

213
Copyright © 2017 Pearson Education, Ltd.
8-38 continued
(b) Catalytic BF3 reacts with trace amounts of water to form the probable catalyst:
F H
dimer
F B O
H H
F H
catalyst

etc.
H H

tetramer trimer
8-39 H—A symbolizes a generic acid.
H
H H H H H
H H
OH OH C A
H A ∆
− H2O H A

alkenes H H H
H C

polymers
(colored)

Note: The wavy bond symbol is used in the following

solutions to indicate the continuation of a polymer chain.

8-40
H H H H H H H H

C C + C C C C C C

H Ph Ph H H Ph Ph H
1° radical, and not resonance-stabilized—
this orientation is not observed

Orientation of addition always generates the more stable intermediate; the energy difference between a 1°
radical (shown above) and a benzylic radical is huge. The phenyl substituents must necessarily be on
alternating carbons because the orientation of attack is always the same—not a random process.

214
Copyright © 2017 Pearson Education, Ltd.
8-41 Each monomer has two carbons in the backbone, so the substituents on the monomer will repeat
every two carbons in the polymer. Wavy bonds indicate continuation of the polymer chain.
Cl Cl Cl Cl Cl Cl Cl Cl Cl

CH2CHCH2CHCH2CHCH2CH
polyvinyl chloride, PVC

F F F F F F F F F F F F F F F
F C C C C C C
F
F F F F F F F F F F F F F F F F
F polytetrafluoroethylene, PTFE, Teflon®
N N N N N N N N N

C C C C C C C C C

CH2CHCH2CHCH2CHCH2CH
polyacrylonitrile, Orlon®

8-42
O O O

H COCH3 H C OCH3 H C OCH3

HO C C HO C C HO C C
H Me H Me H Me
O

H COCH3
C C
H Me
O O
COOMe COOMe
H H C OCH3 H H C OCH3

HO C C C C HO C C C C

H Me H Me H Me H Me
etc.

COOCH3 COOCH3 COOCH3 COOCH3 COOCH3

Wavy bonds mean that the chain continues. Plexiglas®

215
Copyright © 2017 Pearson Education, Ltd.
8-43 The accepted mechanism of olefin metathesis includes an intermediate with a four-membered ring where
one of the atoms in the ring is the metal catalyst, abbreviated [M]. All steps are equilibria.
catalyst
H H3C H
[M] CHCH3
CH3 [M] C
Step 1: + [M] +
C C
H CH3 H H H H H CH3
C C H CH3 cis and trans
H H

catalyst
H H H
[M] CH2
H [M] C
Step 2: + [M] +
C C
H H H H H CH3 H H
C C H3C H catalyst is
regenerated NEW PRODUCTS
H3C H

8-44 An excellent discussion of the olefin metathesis reaction is available at the Nobel Institute website:
http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2005/ then click on Advanced Information

The catalyst needs to have the short end of the molecule attached to the metal:

+ [M] [M] CHCH2CH3

catalyst
O [M]
+ O CH3
liquid O
+
O CH3
gas E+Z

Unnumbered problem in the Problem-Solving Strategy section:

O Br2 or
OH O
H3C C OOH Na Br NBS

H3 O+ OH OH hν
plus the enantiomer
O
O

O
mCPBA OH

OH
plus the enantiomer 216
Copyright © 2017 Pearson Education, Ltd.
8-45 In the spirit of this problem, all starting materials will have six carbons or fewer and only one carbon-
carbon double bond. Reagents may have other atoms.
(a)
Br2 Br C N C N
hν
(or NBS)
major product from resonance
(b) stabilized radical on 1° and 3° C
OH O
BH3 • THF H2O2 Na Br Br2

CH3 HO– CH3 hν

CH3
anti-Markovnikov (or NBS)
syn stereochemistry

O O
plus the CH2I2
enantiomer
CH3 Zn, CuCl CH3

(c) Br2 Br KOH Br2 Br KOH OH

∆ hν Only substitution
Br (or NBS) is possible.
Na

mCPBA O
O

OH
O H2O

8-46 All chiral products in this problem are racemic mixtures. CH3
H CH3
Cl CH3 H
(a) (b) (c)
Br BH2 OH
H
Br
intermediate
Br
Cl
H O
+ O
(d) (e) (f) (g)
O
trans
Peroxides do not
affect HCl addition.

CH3 CH3 CH3

(h) (i) OH (j) OH (k) O
OH
OH O
OH OH
217 OH
Copyright © 2017 Pearson Education, Ltd.
8-46 continued

CH3
(l) O (m) H (n) (o)
+ CH2
O H CH2
CH3 OH
H

(p) NaBH4 (q)

HO OH HO
HgOAc Cl
intermediate

8-47 HO O
OH O O O
(a) CH3 (b) CH3 O (c) H + CH2 O

HO O HO
HO
HO OH O O HO OH
(d) OH (e) + CO2 (f) OH
CH3 CH3
Br
Br Br
(g) (h) Br (i)

Br Cl
HO Br Cl Cl CH3O
(j) OH (k) Cl (l) OCH3
CH3 CH3
Br
Br Br
(m)
CH3 Br

8-48 Recall these facts about ozonolysis: each alkene cleaved by ozone produces two carbonyl
groups; an alkene in a chain produces two separate products; an alkene in a ring produces one product
in which the two carbonyls are connected.
(a) (b)

218
Copyright © 2017 Pearson Education, Ltd.
8-48 continued
(c) (d)

8-49 Chiral products in this problem are racemic.

CH3
CH3CO3H OH
(a)
H2O
OH

OsO4 OH CH3CO3H
(b)
H2O2 OH H2O
(or cold, dilute KMnO4)
cis + syn trans + anti
(cis double bond plus (trans double bond plus
syn stereochemistry of addition) anti stereochemistry of addition)

Br2 1 Br Anti addition of Br2 requires trans alkene to

(c) 2 give meso product.
2
Br
1
This structure shows rotate around C-2
a trans alkene in a
10-membered ring, Br
1
just the rotated view 1
H H
of the structure to 2 Br2 2
the right. Br

trans-cyclodecene

Cl2 Cl BH3 • THF H2O2

(d) (e)
H2O HO−
OH
H
OH
Hg(OAc)2 NaBH4
(f) or or
CH3OH
OCH3
Br
8-50
(a) Br2 , hν Even though this product comes from an allylic radical intermediate
with the possibility of two products, the major product is this one,
or NBS with the double bond in the more stable tetrasubstituted position.

219
Copyright © 2017 Pearson Education, Ltd.
8-50 continued
Br OH
Br
(b) H2O, ∆ (c) Br2 CH3 plus the
enantiomer
SN1 conditions anti Br
from (a) (Avoid KOH that would do E2.) addition CH3

CH3 OH
(d) KMnO4 OH (e) HCO3H CH3
HO– OH H3O+ OH
cold, dilute CH3 CH3
anti addition
or OsO4, H2O2 plus the
syn addition enantiomer
Br CH3
(f) CH3 KO-t-Bu, ∆ (g) Br2, H2O OH plus the
Br E2 conditions CH3 enantiomer
CH3 Br
from (c) or Et3N, a bulky, hindered base a bromohydrin
CH3 CH3
(h) OH KOH, ∆ OH (i) KMnO4 O
CH3 E2 HO– , ∆ O
Br conditions
from (g) or (1) O3 at –78 °C, (2) Me2S

8-51
Hg(OAc)2 NaBH4 HBr
(a) (b)
H2O OH ROOR
Br

1) BH3 • THF 1) O3, –78 °C; 2) Me2S

(c) (d) O
2) H2O2 , HO− or KMnO4, heat
OH

Hg(OAc)2 NaBH4 OsO4 OH

(e) (f)
CH3OH OCH3 H2O2
OH
or cold, dilute KMnO4

CH2I2 Cl2 Cl
(g) (h)
Zn(Cu) H2O
OH
CH3 O
(i) HBr KOH mCPBA
Br
heat

Alternatively, hydration followed by dehydration to methylcyclopentene would give the same product.
220
Copyright © 2017 Pearson Education, Ltd.
8-52 new bonds
OCH3 new bonds
(a) (c)
H3CO
+ H2C CH2 CH2OH
O H2C CH
OH
O
new bonds
O
(b)
+ H2C CH2
O
O

8-53 [M] CHR Z+E

+ H2C CH2
(a) 2
[M] CHR
(b) +
Z+E Z+E
Ring-opening metathesis: the 4 carbons from cyclobutene become the middle 4 carbons of the product.
8-54 O O
O
(a) (b) + O CH2
t-Bu

O H (CH2)4COOCH3 O
(c) + (d)
O + O CH2
H (CH2)4CH3 O

8-55
(a) Br
Br2 excess NH3
NH2
H 2O SN2
A OH B OH
bromohydrin

(b) (1) Hg(OAc)2, H2O H2SO4 OsO4 OH

OH heat H 2O 2 OH
(2) NaBH4

C D E

221
Copyright © 2017 Pearson Education, Ltd.
8-55 continued

(c) excess
excess HBr KO-t-Bu
Br
ROOR heat
anti- hindered base 1. excess O3, –78 °C
Markovnikov gives less substituted 2. (CH3)2S
Br F double bond G
O

O
O
H
(d) "Ph" is the abbreviation for a phenyl group.
OH
Br
Ph Br2 KOH Ph Ph
Ph 1) excess BH3•THF
heat 2) H2O2, NaOH
Br
K OH
J
L
8-56 (a)
initiation

RO OR 2 RO •

RO • + H Br ROH + Br •

propagation
H Br Br
H H
Br • + C + H Br + • Br
H

(b) H H
H
C
H O H O H O H O H OH
H H H
H

222
Copyright © 2017 Pearson Education, Ltd.
8-56 continued
(c) H H H H H
H H hydride
H H Br C H C H shift H
OR C
H H H H
H H H H
2° carbocation 3° carbocation

Br Br

Br Br
from unrearranged from rearranged
carbocation carbocation

(d) Br Br
HO– + H C Br C Br Br− + CBr2
Br Br
Br
Br

+ CBr2

(e) Br Br Br Br
H Cl Cl
C C C
Cl

H H H
H H
OR
Br Br
Br Br
C C HOEt
Et Et
C C
O HOEt O
H H H
H H H
H

(f) H
O H A O HO H CH2CH3
CH3CH2 H CH3CH2 H CH3CH2
H CH2CH3 H CH2CH3 O H H O H
H H
Water could attack either
carbon with the same results. O H
CH2CH3 HO OH H
H H H CH2CH3
H OH rotate HO
H OH CH3CH2
CH3CH2 CH2CH3 OH
CH2CH3 H

223
Copyright © 2017 Pearson Education, Ltd.
8-56 continued
(g) OH OH
H A H
O O
O CH3 O CH3
O H O CH3
Methanol could attack either H H3C H racemic mixture
carbon of the epoxide but it
must attack from the opposite
side of the ring.

(h) H H H H
H H
H H A HC H H H3C H A H3C H
H 3
C H C
H
Ph Ph Ph Ph Ph Ph Ph

Recall that "Ph" is the abbreviation for phenyl.

8-57
The slow step is the first step, formation of the carbocation, in electrophilic addition. The major product
is the one whose intermediate carbocation is formed faster, as it has the lower activation energy. Assume
that the energy of the products will be roughly the same, and both pathways begin with the same
reactants, so the only difference occurs in the transition states and the intermediates.
anti-
H
H
Markovnikov C

2°
energy

3°
Markovnikov
+ HBr H
H
C H
C
H Br
Br
C H
H
reaction
formed faster
8-58 Once the bromonium ion is formed, it can be attacked by either nucleophile, bromide or chloride,
leading to the mixture of products.
Br Br
Br Br H
Br
H H H H H Br

Br Br H
Cl
H H H Cl
224
Copyright © 2017 Pearson Education, Ltd.
8-59 Two orientations of attack of bromine radical are possible:
(A) anti-Markovnikov
H
HBr
+ • Br C + • Br
Br Br
3° radical
(B) Markovnikov
Br Br
HBr
+ • Br CH2 + • Br
H
1° radical

The first step in the mechanism is endothermic and rate determining. The 3° radical produced in anti-
Markovnikov attack (A) of bromine radical is several kJ/mole more stable than the 1° radical generated
by Markovnikov attack (B). Hammond's Postulate tells us that it is reasonable to assume that the
activation energy for anti-Markovnikov addition is lower than for Markovnikov addition. This defines
the first half of the energy diagram.
The relative stabilities of the final products are somewhat difficult to predict. (Remember that
stability of final products does not necessarily reflect relative stabilities of intermediates; this is why a
thermodynamic product can be different from a kinetic product.) From bond dissociation energies
(kJ/mole) in Table 4-2:
anti-Markovnikov Markovnikov
H to 3° C 403 H to 1° C 423
Br to 1° C 303 Br to 3° C 304
706 kJ/mole 727 kJ/mole

If it takes more energy to break bonds in the Markovnikov product, it must be lower in energy,
therefore, more stable—OPPOSITE OF STABILITY OF THE INTERMEDIATES! Now we are ready to
construct the energy diagram.
Br
CH2
Markovnikov
1°
energy

3°
anti-Markovnikov

C
Br Br

Br

reaction
It is the anti-Markovnikov product that is the kinetic product, not the thermodynamic product; the anti-
Markovnikov product is obtained since its rate-determining step has the lower activation energy.

225
Copyright © 2017 Pearson Education, Ltd.
8-60
A) Unknown X, C5H9Br, has one element of unsaturation. X reacts with neither bromine nor KMnO4,
so the unsaturation in X cannot be an alkene; it must be a ring.
B) Upon treatment with strong base (tert-butoxide), X loses H and Br to give Y, C5H8, which does
react with bromine and KMnO4; it must have an alkene and a ring. Only one isomer is formed.
C) Catalytic hydrogenation of Y gives methylcyclobutane. This is a BIG clue because it gives the
carbon skeleton of the unknown. Y must have a double bond in the methylcyclobutane skeleton, and X
must have a Br on the methylcyclobutane skeleton.
D) Ozonolysis of Y gives a dialdehyde Z, C5H8O2, which contains all the original carbons, so the
alkene cleaved in the ozonolysis had to be in the ring.

Let's consider the possible answers for X and see if each fits the information.
Br KO-t-Bu O
ozonolysis
1)
O CH2
if this is X this could be Y; DOES NOT FIT OZONOLYSIS RESULTS
only one product so this cannot be X and Y.
KO-t-Bu Y would be a mixture of alkenes, but the elimination
2)
Br gives only one product. We already saw in example 1
if this is X major minor that the exocyclic double bond does not fit the
ozonolysis results so this structure cannot be X.

KO-t-Bu Y would be a mixture of alkenes, but the elimination

3)
gives only one product, so this structure of X is not
major minor consistent with the information provided.
Br
if this is X

KO-t-Bu ozonolysis
4)

Br SAME COMPOUND; O O
if this is X this could be Y; Z, a dialdehyde
only one product

The correct structures for X, Y, and Z are given in

the fourth possibility. The only structural feature of
X that remains undetermined is whether it is the cis
? ?
or trans isomer. Br Br
cis trans

8-61 The clue to the structure of α-pinene is the ozonolysis. Working backwards shows the alkene position.
O became carbonyl carbons
backwards
α-pinene
H O

continued on next page

226
Copyright © 2017 Pearson Education, Ltd.
8-61 continued
After ozonolysis, the two carbonyls are still connected; the alkene must have been in a ring, so reconnect the
two carbonyl carbons with a double bond.
Br Br
Br2
or
CCl4 Br CH3
CH3 Br
A A
Br Br
Br2 H2SO4
Zaitsev product Bredt's Rule: no
H2O OH ∆ double bond at
CH3 bridgehead
B C
OH
PhCO3H H3O +
O
OH

D E
8-62 The two products from permanganate oxidation must have been connected by a double bond at the
carbonyl carbons. Whether the alkene was E or Z cannot be determined by this experiment.
CH3(CH2)12CH CH(CH2)7CH3
shown here as Z, the naturally occurring isomer

8-63
3 H2 must have three alkenes
Unknown X in this skeleton
Pt

O O O O
O3 Me2S
Unknown X CH2 O + +
H H
O
There are several ways to attack a problem like this. One is the trial-and-error method, that is, put double
bonds in all possible positions until the ozonolysis products match. There are times when the trial-and-error
method is useful (as in simple problems where the number of possibilities is few), but this is not one of them.

Let's try logic. Analyze the ozonolysis products carefully—what do you see? There are only two methyl
groups, so one of the three terminal carbons in the skeleton (C-8, C-9, or C-10) has to be a =CH2 . Do we
know which terminal carbon has the double bond? Yes, we can deduce that. If C-10 were double-bonded to
C-4, then after ozonolysis, C-8 and C-9 must still be attached to C-7. However, in the ozonolysis products,
there is no branched chain, that is, no combination of C-8 + C-9 + C-7 + C-1. What if C-7 had a double
bond to C-1? Then we would have acetone, CH3COCH3, as an ozonolysis product—we don't. Thus, we
can't have a double bond from C-4 to C-10. One of the other terminal carbons (C-8 or C-9) must have a
double bond to C-7.
2 3 2 3
8 8
1 4 1 4
7 10 7 10
9 9
6 5 6 5

continued on next page 227

Copyright © 2017 Pearson Education, Ltd.
8-63 continued
The other two double bonds have to be in the ring, but where? The products do not have branched chains,
so double bonds must appear at both C-1 and C-4. There are only two possibilities for this requirement.

I or II

Ozonolysis of I would give fragments containing one carbon, two carbons, and seven carbons. Ozonolysis
of II would give fragments containing one carbon, four carbons, and five carbons. Aha! Our mystery
structure must be II.

Note to the student: Science is more than a collection of facts. The application of
observation and logic to solve problems by deduction and inference is a critical
scientific skill, one that distinguishes humans from algae.

8-64 In this type of problem, begin by determining which bonds are broken and which are formed. These
will always give clues as to what is happening.

H
H O H
formed
H+ goes to most
O O electronegative H O
atom.
broken
Protonated epoxide opens to give
the most stable carbocation (3°).

H
H
H O
C
3° carbocation looks
C for electrons, finds
HO HO H O them at nearby alkene,
forming a 6-membered
ring (yes!)—leaves a
3° carbocation.

8-65 See the solution to Problem 8-35 for simplified examples of these reactions.
COOH HO OH
OsO4
(a) trans + syn → racemic
H2O2 H
HOOC HOOC
H COOH

COOH HOOC H OH
CH3CO3H
(b) trans + anti → meso
H2O COOH
HOOC HO H
228
Copyright © 2017 Pearson Education, Ltd.
8-65 continued
HOOC H OH
COOH CH3CO3H
(c) cis + anti → racemic
H2O H
COOH HO COOH

COOH HO OH
OsO4
(d) cis + syn → meso
H2O2 COOH
COOH HOOC
H H

8-66 D
1) BD3 • THF
CH3
2) H2O2, NaOH OH
H

8-67 By now, these rearrangements should not be so "unexpected".

H 2°
H Br C H

CH3 H
H Alkyl migration with ring
expansion gives 3° carbocation in 6-
membered ring—carbocation
nirvana!
H
H
CH3
H

Br Br C
CH3
CH3

You must be asking yourself, "Why didn't the methyl group migrate?" To which you answered by drawing
the carbocation that would have been formed:
H 2° 3°
C H
C CH3
CH3 H CH 3
H
The new carbocation is indeed 3°, but it is only in a 5-membered ring, not quite as stable as in a 6-
membered ring. In all probability, some of the product from methyl migration would be formed, but the 6-
membered ring would likely be the major product.

229
Copyright © 2017 Pearson Education, Ltd.
8-68 Each alkene will produce two carbonyls upon ozonolysis or permanganate oxidation. Oxidation of
the unknown generated four carbonyls, so the unknown must have had two alkenes. There is only one
possibility for their positions.
H H
COOH
KMnO4 O O
+
heat HO C C OH
COOH
H H
the unknown

8-69
(a) Fumarase catalyzes the addition of H and OH, a hydration reaction.
(b) Fumaric acid is planar and cannot be chiral. Malic acid does have a chiral center and is chiral. The
enzyme-catalyzed reaction produces only the S enantiomer, so the product must be optically active.
(c) One of the fundamental rules of stereochemistry is that optically inactive starting materials produce
optically inactive products. Sulfuric-acid-catalyzed hydration would produce a racemic mixture of malic
acid, that is, equal amounts of R and S.
(d) If the product is optically active, then either the starting materials or the catalyst were chiral. We
know that water and fumaric acid are not chiral, so we must infer that fumarase is chiral.
(e) The D and the OD are on the "same side" of the Fischer projection (sometimes called the "erythro"
stereoisomer). These are produced from either: (1) syn addition to cis alkenes, or (2) anti addition to
trans alkenes. We know that fumaric acid is trans, so the addition of D and OD must necessarily be anti.
(f) Hydroboration is a syn addition.
H COOD
1. BD3 • THF D OD DOOC H
HOOC H +
C C 2. D2O2, DO− DOOC H D OD
H COOH H COOD
COOD COOD
(Note that OH exchanges
H OD DO H
with D in DO−.)
D H H D
COOD COOD
As expected, trans alkene plus syn addition puts the two groups on the "opposite" side of the Fischer
projection (sometimes called "threo").

8-70 Hg(OAc) Hg(OAc)

HgOAc
(a)
OH Hg(OAc) OH O H O

AcO
mercurinium ion
NaBH4

230
Copyright © 2017 Pearson Education, Ltd.
8-70 continued
(b)
Br Br
Br Br
Br

OH OH O H Br O

bromonium ion C7H13BrO

8-71
This mechanism is very similar to formation of a halohydrin (text Mechanism 8-8); the difference is that
the nucleophile comes from the carboxylic acid on the other side of the molecule, making a new ring in
the process.
Step 1: formation of the iodonium ion;
Step 2: internal nucleophilic attack (the O of the C=O is more nucleophilic than the OH because of
resonance stabilization of the intermediate);
Step 3: removal of the proton by H2O. H H
O O O O
O C O C
OH OH
I I I

Large I2 will approach from the I I

side opposite the large COOH
group.
H
O O
O C O C
H2O

I I

8-72 For clarity, the new bonds formed in this mechanism are shown in bold.
H CH3
RO OR 2 RO•
H CH HH C C C H CH3 H CH3
3 3

RO H H
+ C C RO C C RO C C C C
H H H H H H H H

H CH3 H CH3 H CH3 H CH3

etc. RO C C C C C C C C
H H H H H H H H
231
Copyright © 2017 Pearson Education, Ltd.
8-73 Without divinylbenzene, individual chains of polystyrene are able to slide past one another.
Addition of divinylbenzene during polymerization forms bridges, or crosslinks, between chains, adding
strength and rigidity to the polymer. Divinylbenzene and similar molecules are called crosslinking
agents.

Ph Ph Ph Ph Ph Two polystyrene chains crosslinked

by a divinylbenzene monomer shown
in red.
Ph Ph Ph Ph Ph

8-74 A peroxy radical is shown as the initiator. H CH3

Newly formed bonds are shown in bold.
H CH3 H CH3 C C H CH3 H CH3
RO H CH3
+ C C RO C C RO C C C C
H CH3 H CH3 H CH3 H CH3

H CH3 H CH3 H CH3 H CH3

etc. RO C C C C C C C C
H CH3
H CH3 H CH3 H CH3

8-75
tetrasubstituted,
esters—not typical
hindered
H3CO OCH3 H3CO OCH3
1) 2 O3 at –78 °C

2) (CH3)2S O O

O O
H H

aldehydes—expected
8-76
The stability of the intermediate formed in the first step determines the orientation. S
C
SCH3 S H H
H+ H+
C C H +
H
H H S
3° carbocation is more 3° carbocation
stable than secondary; is still good C
explains Markovnikov
orientation. H H
232 RESONANCE STABILIZED!
Copyright © 2017 Pearson Education, Ltd.
8-77 The addition of BH3 to an alkene is reversible. Given heat and time, the borane will eventually
"walk" its way to the end of the chain through a series of addition-elimination cycles. The most stable
alkylborane has the boron on the end carbon; eventually, the series of equilibria leads to the ultimate
borane product that is oxidized to the primary alcohol.
BH2
BH3

∆
dec-5-ene H
∆
H

BH2 + BH3
∆
BH2

+ BH3 H
∆
H

BH2 + BH3
∆
BH2

+ BH3 most stable H

H2O2, HO−
OH

decan-1-ol

233
Copyright © 2017 Pearson Education, Ltd.
8-78 First, we explain how the mixture of stereoisomers results, then why.
We have seen many times that the bridged halonium ion permits attack of the nucleophile only from the
opposite side.
Cl Cl
expected: Cl Cl Ph
Cl
H Ph H Ph H Cl
trans only
(plus the enantiomer)
A mixture of cis and trans could result only if attack of chloride were possible from both top and bottom,
something possible only if a carbocation existed at this carbon.
actual:
Cl Cl
Cl Cl Cl Ph + Cl Cl
C
H Ph H Ph H Cl H Ph
trans cis

Cl
This picture of the p orbitals of benzene shows
H resonance overlap with the p orbital of the
carbocation. The chloride nucleophile can form
a bond to the positive carbon from either the top
or the bottom.

Why does a carbocation exist here? Not only is it 3°, it is also next to a benzene ring (benzylic) and
therefore resonance-stabilized. This resonance stabilization would be forfeited in a halonium ion
intermediate.
CH

Cl Cl C C
H
Cl Cl Cl

cis trans HC
Cl Ph
Ph Cl Cl C
+
H H
Cl Cl Cl Cl
plus the enantiomers of each

234
Copyright © 2017 Pearson Education, Ltd.
8-79
(a) The three bonds to boron, indicated by the squiggly line, will be replaced by an OH.

H2O2 7 6 OH
8 5
+
NaOH 1 4
B OH HO 2 3

7 6 5
4
8-membered ring
8 1
2 with OH groups
3 at C-1 and C-5

(b) H
B
1 6 6 5
+ BH3 4
2 5
1
2
3 4
3
(1Z,5Z)-cycloocta-1,5-diene 9-BBN

Note to the student: Chapter 8 introduces a type of graphical reaction summary called a "starburst"
diagram. These are visually helpful in organizing the reactions, and very useful in reviewing before
quizzes and exams. Your instructor may not cover all of the reactions in the chapter, so it would
benefit you to customize the reaction diagrams to optimize their utility for your course.

235
Copyright © 2017 Pearson Education, Ltd.