Name _______________________

I. (29 points) Page 1

Provide the missing materials for each of the following reactions. If you are providing
reagents, be sure to number steps if more than one step is required for the complete
transformation. If any product forms as a stereoisomeric mixture, then draw only one, clearly
showing valid stereochemistry, and write "+ enantiomer" or "+ diastereomer" or "+
stereoisomers" (when more than two stereoisomeric molecules can be drawn).

A. (a) (b)
1. BH 3
2. H 2O 2 /NaOH H 2O/H 2SO4 (cat.)

OH
+ enantiomer 3 3

B. Balance both reactions -1 pt each if any box adds "+ something" when not an answer
(a) (b)
O
CH 3CH2CH2CH 3
1 pt Cl S 2 pts Cl
LiCH 2CH2CH2CH 3 O 1pt
O O
S
O Li 1 pt HO O
2 pts N N
1pt H
4 4

C.
(a) Draw all products; (b) provide reagent(s)
rearrangement is not observed O
OH
1) NaH 2 pts
H 3PO 4 must be in order
2 pts
2) 2 pts
heated H2
2 pts Cl
CH 3 CH 3 CH 3
CH 3
4 4 Na Cl
can be drawn 3d-no stereochem

D.
Br P
P

Provide the complete name (including stereochemical labels as needed) for this starting material

(R,E)-6-bromo-4-methylhept-3-ene
4
 Name _______________________
Page 2
II. (29 points)
Provide all of the missing materials for each of the following reactions. If more than one product
forms, draw each, showing all structural and stereochemical properties unambiguously. Use the
information provided.
A.
1)H 2
OH
PdBaSO 4 (or CaCO 3)
quinoline (or Pb)
2) KMnO 4 HO

B.
Br
Br O
Na
Br
OH
2 each, must be in correct boxes single product
all possible optically inactive all possible optically active
starting materials 6 bimolecular elimination leading only
starting materials to thermodynamic product
C.
O (S) O (R) O
(R) O
O
O H (S) (R)
(R) (S) (R)
excess (S) (S)
O (R)
O
(S) O
3 each, must be in correct boxes
optically inactive optically active
product(s) product(s) 6

D. (a) Draw all products expected to form

O note that the OH goes to the
O O more substituted side,
OH creating a chiral center, Cl
Cl OH OH OH goes to the bottom, not
OH OH chiral, but can be drawn 3D
Cl Cl
must
be 3D 4
(b) The reaction shown directly above yields completely different products under alkaline
conditions (notice the acidic proton is now removed in the starting material), when using I 2 to
form the predicted halonium intermediate. Ignoring stereochemistry, draw a complete curved
arrow mechanism for the formation of this product.

O O

O O
O
O
I I I

return arrow can go to I

either C of the pi bond 3 pts intermediate (all or nothing with charge)
3 points for each mechanism - no partial, all arrows
9
 Name _______________________
III. (24 points) Page 3
Reaction Pairs: In this set of reaction pairs, one starting material is treated with two different
reagents. Please draw only one main organic product (e.g. only the main regioisomer when
regioselection applies), clearly showing in your drawing all structural and/or stereochemical
information as needed; ignore all reaction byproducts as usual. Then discuss the total number
of product(s) expected to form by checking the box(es) that apply.
A.
Draw one product
Draw one product

HO
HO HO OH
HO H H2 OH
HO H H 2O or
or Pd/C
must show H 3D... H 2SO 4 (cat.) 4
4
This product will form with (check all that apply)
This product will form with (check all that apply)
one or more structural isomer(s)
one or more structural isomer(s)
one or more stereoisomer(s)
X one or more stereoisomer(s) must have product correct for 3 X
in order to get 1 pt each below no other products - alone
no other products - alone

B.
Draw one product Draw one product

Br
(S)
(S) (S)
(R) (R)
(R) OH Br 2
OH KMnO 4 Br
OH
OH
or meso compound only
any conformation
non-meso compound only 4
4
This product will form with (check all that apply)
This product will form with (check all that apply)
one or more structural isomer(s)
one or more structural isomer(s)
one or more stereoisomer(s)
X one or more stereoisomer(s) must have product correct for 3
no other products - alone in order to get 1 pt each below X no other products - alone

C.
Draw one product Draw one product

OH
OH H or
or 1) B 2H 6
CH 3OH
Br Br H 3CO H 3CO
2) H 2O2/NaOH
OH can go to either C only C12 H 22O product(s) observed 4
ring C must be drawn 3D 4
Br
This product will form with (check all that apply)
This product will form with (check all that apply)
one or more structural isomer(s)
X one or more structural isomer(s)
must have product correct for 3 X one or more stereoisomer(s)
X one or more stereoisomer(s) in order to get 1 pt each below no other products - alone
no other products - alone
 Name _______________________
IV. (28 points) Page 4

A. Complete the following synthetic pathway by supplying the missing structures. In all cases,
stereochemistry should be ignored.
must have both products
The first reaction yields (c) completely correct for 3
only structural isomers, points; no partial
2 and 3 O O
(a) C7H13BrO O O3
O
N Zn
H
O 2
Br N 2 H
+ must have both products
a strong, bulky base (d)
(b) draw product 3 completely correct for 3
O points; no partial
1 2
O3 O
CH 3
O
H 2O2/NaOH O
CH 3
2
3 3
B. When Compound 2 is treated with methanol under
acidic conditions, rearrangement occurs before the CH 3
final addition products are observed. The formation
of 4 or 5 can be explained with one rearrangement O CH 3OH O O
+ 5
step, and either shift leads to the formation of a H 2SO 4 (cat.)
resonance stabilized carbocation intermediate.
Show the complete multi-step mechanism for the 2 4
formation of 4. You should show and use this
intermediate in your mechanism. Choose your
acid/conjugate base wisely. Ignore stereochemistry.
(a) Draw the most straightforward curved-arrow mechanism for formation of 4 from 2.
arrow from O is optional - goes to major res. form CH 3
1 O 4 O O
O H
5
2
H 3
H CH 3
O
O
O CH 3 O O
CH 3 H

1 O 4
O
2 CH 3
5 H
3
2 pts each intermediate only the major resonance must be shown
2 pts each mechanistic step (must choose correct acid/base)
grading stops with first irrational step 14

(b) Now provide the (c) For each connectivity, state the number of
molecules represented (i.e. stereoisomers).
structure of 5, a structural
isomer of 4, also formed via O CH 3
a single rearrangement step O
2 O O 2
that leads to a resonance OCH 3
stabilized intermediate. 5 3 1 pt each 2
 V. (30 points) Name _______________________
Page 5
Reaction Pairs Redux. Each of these reactions yields a single product. However, the
pair of reactions illustrates an aspect of selectivity, showing how different product(s)
result from isomeric starting materials. Examine this concept by providing the missing
information.
A.
(iii) The single product
(ii) The single product

Na Na
H
H NH 3 NH 3
H excess excess
H

(i) How are these two starting materials related?

3 3
structural (or constitutional) isomers 2

B. (iii) Draw a Newman projection

(ii) The single product showing the conformation favored
for this type of reaction. The C with
the leaving group should be in front.
CH 3
CH 3 OK
(S) (Z)
O
(S)
H 3C S O H
O
3 MsO H
(i) How are these two starting materials related? CH 3 3
diastereomers 2
(v) Draw a Newman projection
O (iv) The single product showing the conformation favored
for this type of reaction. The C with
H 3C S O the leaving group should be in front.
(S) OK
O (R) (E)
CH 3

H CH 3

3 H OMs
wrong connectivity 0 3
stereochem wrong 0
conformation wrong +2
C. 1) O N 1) O (iii) Main organic product
(ii) Main organic product OH Cl S CH 3 N
Cl S CH 3
(Z) (R)
O O
NaCl SCH 3
(Z)
2) CH 3SNa 2) CH 3SNa (S)
(S) (Z)
OH
(R) (Z)
SCH 3 (i) How are these two starting materials related? 3
3
enantiomers 2