California State University Long Beach Organic Chemistry Worksheet

Problem Set #1Review of Fundamental Reactivity
1. Provide the expected major product for each reactions or reaction sequences.
(a)
1. Br2, MeOH
2. KOtBu
O
(b)
OH
1. SOCl2
2. AlCl3
Br
(c)
1. Mg, Et2O
2.
O
OMe
3. H2SO4, Δ
(d)
O
O
NaBH4 then H2O
OMe
(e)
1. NaOH, H2O
O
2. TsCl, pyridine
O
(f)
3. NaCN, DMSO
O
O
1. LiAlH4 then H+/H2O
2.
O
, H+
2. Nitriles are useful functional groups. They can be easy way to introduce a carboxylic
acid into a molecule. Propose a reasonable a mechanism for the reaction below.
O
Br
1. NaCN
OH
2. H+, H2O, Δ
Using this transformation above, provide two syntheses for the transformation below.
One synthesis should use a Grignard strategy and the other should use a nitrile strategy.
O
HO
O
3. In your previous courses, you learned how make and hydrolyze an enamine. Let’s
practice our hydrolysis mechanism.
N
O
H+, H2O
N
H
H
An enol ether is a closely related functional group that we will see this semester. It also is
very acid-sensitive and will hydrolyze under acidic conditions. Provide the expected
products and a mechanism for enol ether hydrolysis.
OCH3
H+, H2O
4. Below is an alcohol dehydration. On a secondary alcohol, this will proceed through a
carbocation. Provide the product and a full arrow-pushing mechanism for this
transformation.
OH
H2SO4
Considering the reaction above, how would you propose to complete the transformation
below? Provide a synthetic route.
OH
O
5. Let’s practice some enolate chemistry. Provide a mechanism for the transformation
below.
Me
O
O
O
Me
O
O
NaOMe, MeOH, Δ
OMe
OMe
HO
OH
Hint: To start, deprotonate the most acidic proton and attack the ester carbonyl carbon.
Look at the substituted benzene as a series of enols
6. Provide an efficient synthesis for each of the following transformations.
(a)
H
O
(b)
O
NH2
OH
(c)
Br