CHEM24

1.

Dr. Spence

Doestheadditionof HBr to the following alkenegive synaddition,anti additionor a mixtureof

both? Briefly explainyour answerusingthe structureof the intermediateformedin this addition.
Hodwhy is this differentfrom additionof Br2? H2?

ftcocluce.l q
DF bo+rh
nng\,.(
z

'

bt,

HBr
-+

(-\o

"'n'*.u^Li

Ll. 5l^ "*Vl

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Vtct Rt rntecrnedi a\t-

w9

[,',ffr

**_)

r." H

Carr c'ctd lu
eitter Fu*g oC

+
..r. fl

(t

Rank the following compoundsfrom most reactive (1) to leastreactive (4) towards 03. Also
rank their reactivity towards BH3. Briefly explain yoril answers.

n
"t

l l n

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o ry
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bsl r- |

rb03

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7

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fe.4.i'r(- to. {7rf,

In the additionof electrophilesto alkenes,most electrophileswill add to the most reactivealkene

first (most electronrich alkene). The two exceptionsto this generalizationarcH2 and BH3.
Provide the productswhen the following alkenereactswith the two reagentsshown below. Be
sureto draw correct stereochemistrywhere necessaryand explain why the electrophileaddedto
the positionyou indicated.
1. BH3 (1 equiv)
Br2 (1 equiv)

2. H2O2,-OH

Z..ttp i5 rvrD(telec*.nan cr,c,h

'ff'tana-5,ti4,)
i:

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h,tt&..<J |}aoa

CHEM24

Dr. Spence

Preparationof Alkenes. The main way to preparean alkene is to perform

an elimination reaction
of an alcohol (via carbocation)or an alkyl halide. For the two reactions
shown below draw all
possibleproducts and then circle the one that is favored under
thermodynamic conditions. We
will seemechanismsfor thesereactionsin a later chapter.
I

1t\,.C1

t_J

strongbase

ft

CHEM24

--t''\

L__l

Dr. Spence

'a
+

OH
H*, H2o

a\/,

LQ-r-r

t
\

oI

cH3-oA

ol l

r R-c-oH
Coccff{J

( onz 5lRf )

d::fl
,'_-r,

{a

H.ij

CHEM24

8.

Dr. Spence

Reactions. Give the structureof the major organicproduct(s)expectedfrom eachof the

following reactions.If necessary,indicateproductstereochemistry.

u(*ronzkQL

.J

l. OsOa

-----------..-_2. NaHSO3
3. HIO4

/'-Jl/\
fL._",4-J )

tBu

,-Ja,

+,r
txt

t)

),,-ll
I

1. RCO3H (1 eq)
2. Brt, HrO

\--\-.2

(CH3)3C p

a*Y'n'
\-.\-,/

l HBr (l equiv)
2. H2,Pil/C

l . H g ( O A c ) 2 ,H 2 O

2. NaBHa

*Y
- $ t

or{
1 RCO3H
2. H-,H2O

Lj-/

a.

OH
1. 03 (l eq)
2. Zn,H+
3. BH3
4. H2O2,HO'

lle.( I

Ort ,

AAr/-/'
0Y|
t 4r"\

trod

9. Supply the missing reagent, reactant, or product. If more than one product can formed, give all
possible products, and indicate which would be the major product. Be sure to indicate the
stereochemistry and regiochemistry of the products where appropriate. The last three are
particularly challenging.
a.
H

1. BH3-THF

OH

2. NaOH, H2O2

syn addition of H, OH

b.
Br
NaOCH3

we used NaOH in class

c.
H2, Pd/C

note: these conditions only reduce ordinary alkenes -- not carbonyls or benzene rings
d.
OH

1. Hg(OAc)2, H2O
2. NaBH4

e.
H

1. O3
2. Zn, HOAc

f.
H 2O
CH3

CH3
H2SO4

OH

carbocation intermediate at more substituted carbon, so OH ends up there

g.
OH

Br2, H2O

Br

anti addition (but product is racemic mixture)

h.
OH

1. BH3-THF
2. NaOH, H2O2

note that 1-butene would give 1-butanol, not 2-butanol as given

i.
Br

Br2

Br

anti addition (but product is racemic mixture)

j.
H2, Pd/C

H2 gas always in excess, so both bonds will react

k.
1. OsO4 (excess)
2. NaHSO3

HO

OH

HO

OH

HO

OH

+
HO

OH

major product

syn addition for each diol; second addition more likely from opposite side
l.
1. O3

2. Zn, HOAc
O

ozone always in excess; 2 moles of each product are formed

m.
H3C
H3C

CH3

H3C
1. BH3-THF

CH3
CH3

H3C

CH3
CH3
CH3

2. NaOH, H2O2
H
OH

borane addition from less sterically-hindered side of alkene

10. Give the missing products, reactants, or reagents for the following reactions.
a.
1) OsO4

OH

2) NaHSO3

OH

b.
OH

1) BH3, THF
2) HOOH, -OH

don't worry about

THF, just a solvent
c.
H2, PtO2

we use Pd/C in class

d.
O

1) O3
2) Zn, H3O+

e.
Br
Br2, CCl4
Br

don't worry about CCl4, just

solvent
f.
Cl
HCl
+
Cl

and likely get a third product via carbocation rearrangement

g.
Br
OH
Br2, H2O

h.
OH

1) Hg(OAc)2, H2O
2) NaBH4

i.
H2, Pd/C

j.
Cl
Cl2, CCl4
Cl

k.
Br2, H2O

OH
Br

l.
1) BH3, THF
OH
2) HOOH, -OH

m.
H2, Pd/C

n.
mCPBA
O

o.
1) O3

2) Zn, H3O+

p.
Cl2, CCl4

Cl

Cl

11. Using mechanistic arrows, draw a detailed mechanism for the following reactions.
a.
I
I

N3

N3

N3

b.
OH

OH2

loss of
H2O

protonation

loss of
H+

hydride
shift

12. Draw a reasonable mechanism to explain the outcome of the following reaction. Be sure that
your mechanism explains the observed stereochemistry.

Br2

Br
O

OH

O
H

Br
Br

Br
O
O
Br

OH

O
H

13. Given the results from the oxymercuration reaction below, predict the products from treating
the same alkene with Br2 and H2O. Draw a mechanism that explains the regiochemistry and
stereochemistry of the product.
H3C

CH3

CH3

H3C
1. Hg(OAc)2, H2O

OH
CH3

2. NaBH4
CH3

H3C

CH3

H3C

CH3

H3C
Br2 , H2O

CH3
OH

CH3

CH3
CH3
Br
Br

bromine must add to bottom face, so water must add from the top

14. Give the stereochemical relationship of the products formed (i.e. enantiomers, diastereomers,
etc) in the reactions below. Recall that the method we use is to look at the products from both top
and bottom face attacks and then to determine the stereochemical relationship between them.
a.
H

1. OsO4, pyridine

CH3

2. NaHSO3

HO

OH

H3C

CH3

HO

OH

H3C

CH3

+
H3C

the two products are the same -- so product is single, achiral, meso compound

b.
H
H3C

CH3

1. OsO4, pyridine

2. NaHSO3

HO

CH3

HO

CH3

H3C

OH

+
H3C

OH
(R, R)

The two products are enantiomers; overall we get a racemic mixture

(S, S)

15. Provide a synthetic sequence to go from the given starting material to the desired product.
Show all reagents and synthetic (not reaction) intermediates. All these syntheses can be
accomplished in two or three steps.
a.

Br

OH
OH

KOtBu

1) OsO4
2) NaHSO3

we use NaOH for step 1 in a

and b and c

b.

Br
O
KOtBu

1) O3
2) Zn, H+

c.

?
Br
Br
KOtBu

HBr

d.

?
OH
OH
1) Hg(OAc)2,
H2O, THF
2) NaBH4

CH3SO2Cl, NEt3

KOtBu
OSO2CH3

don't worry about this

step 1

e.

?
OH
OH
H2SO4

1) BH3, THF
2) HOOH, -OH

f.

Cl

KOtBu

H2, Pd/C

again, we use NaOH in step 1

g.

SCH3

HBr

NaSCH3
Br

don't worry about step 2

h.

I
H
KOtBu

H
1) O3
2) Zn, H+

again, NaOH for step 1

16. Propose syntheses to accomplish the following transformations. Each transformation can be
done in two or three steps.
a.

Br

OH

1) BH3, THF
2) HOOH, -OH

KOtBu

or

1) Hg(OAc)2,
H2O, THF
2) NaBH4

NaOH
step 1
b.
Br

Br

OH

KOtBu

Br2, H2O

NaOH step 1
c.
OH

OH

OH
1) Hg(OAc)2,
H2O, THF
2) NaBH4

CH3SO2Cl,
NEt3
KOtBu
O

SO2CH3

Don't worry about step 1; use NaOH for step 2

or 1) BH3, THF
2) HOOH, -OH

17. Treatment of compound A (C6H14O) with H2SO4 gave two alkene products, with B as the
major product. Catalytic hydrogenation of B gave 2-methyl-pentane as the only product.
Hydroboration (1. BH3-THF; 2. H2O2, NaOH) of B gave a single compound, alcohol C.
Ozonolysis of B gave a ketone and an aldehyde (no formaldehyde): compounds D and E. Show
the structures of all the compounds: A, B, C, D, and E.

H2SO4
Alcohol

H2, Pd/C

A
Alcohol
Dehydration

Alkene

Alkane
1.BH3-THF
2. H2O2, NaOH

OH
1. O3
2. Zn, HOAc

Alcohol C
Alkene B
must be
R

D and E must be:

O
R

O
H

OH