CHEM 234 • Organic Chemistry II • Fall 2020

Discussion activity Week 11 • Amines • KEY

1. Predict the major product(s) for the following transformation:

NH2 F
1. NaNO2, HCl
2. HBF4
Me Me Me Me

NH2 1. NaNO2, HOAc Me

2. CuI

3. Me

SMe MgCl
SMe
cat. Pd(PPh3)4

O
1. NH3, H2,
Me cat. Ni, EtOH
2. MeI (excess), THF
3. Ag2O, H2O
4. heat

1. NaN3, DMF
O 2. H3O+ O
3. H2, Pd/C

4. MeI (xs), THF

Me 5. Ag2O, H2O, MeOH
6. heat

1 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY
1. H
N
H 2N
O O
OMe MeO
H+, MeOH

O 2. xylenes, heat N
H

O
F
HN Me 1. Br2, FeBr2 Cl
2. KOH, H2O
3. NaNO2, HCl, H2O
4. CuCl OMe
OMe

iPr
OH i-Pr
Ph 1. PCC, CH2Cl2
Ph Ph N Ph
OH 2. NH4OH, heat H

1. KOH, H2O
O O
2. Br
H
3. H2NNH2, EtOH N Me
NH
4. cat. Cp2Ln(NMe2), THF
O O

2 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY

1. NaH, DMF Ph
O
Br Ph
Me
2. H2N NH OMe
MeO N
H

cat. H+, MeOH

3. xylenes, heat

H2N Me 1. MeI (excess), THF

H iPr
2. Ag2O, H2O Me N
3. heat
4. cat. (Ph3P)2PdCl2
H 2N iPr

OH
1. heat
NMe3
2. mCPBA, CH2Cl2 OH
Me Me 3. NaCN, DMF
H 2N Me
4. LiAlH4, Et2O
5. H2O

CN
NH2 1. NaNO2, HCl, H2O H
N OMe
Br 2. CuCN, DMF
3. cat. Pd(PPh3)4, KOt-Bu
t-Bu
t-Bu
MeO NH2

3 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY

1. MeI (excess), THF

2. Ag2O, H2O
NH2 3. heat O
4. mCPBA, CH2Cl2 Ph
Me Ph

1. O

NH
S O
S O
KOH, H2O
Br 2. H2NNH2, EtOH NH2
3. HgCl2, H2O

4 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY
2. Provide the reagents to accomplish the following transformations

1. H2, Pd/C
2. NaNO2, HCl
3. NaOH
NO2 OH

O O
O O

1.
Me (excess) O
+
H (aka H2SO4 or
NH2 HN Ph
H3PO4)
iPr iPr

2. or
O O O
iPr
Ph O Ph Ph Cl
CH2Cl2

1. H2NHNPh, MeOH,
cat. H+
O 2. xylenes, heat
H
N

1. H2, Pd/C
2. Ac2O, Py OH O
NH2
3. AcCl, AlCl3
Me

O 4. KOH, H2O O
O 2. NaNO2, HCl O
3. NaOH

5 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY

1.
H 2N

O heat
HN

H Me

t-Bu 2. NaBH3CN, HOAc t-Bu

1. NaBH3CN, HOAc
2. O O
O O
Me Me
N Br N
Ph H Ph
Pd(PPh3)4 (1 mol %)
KOt-Bu, PhMe

1. NaN3, DMF
2, LiAlH4, THF
3. H3O+ H
N Me
O
Br
4 Cp2LaNMe2 (1 mol%) O
THF
or
(Ph3P)2 PdCl2 (cat)
THF

1. NH3, Ni, H2, EtOH

2.

O HN Me
Br Me
Me Me

Pd(PPh3)4 (1 mol %)
KOt-Bu, PhMe

6 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY
3. Using retrosynthetic analysis, provide a synthesis for the following molecule. Place the required
reagents next to the arrows and the necessary intermediates in the boxes provided.

H O O
Me N
Me N

Cp2LnNMe2 (1 mol %)
THF NH2, Ni, H2, EtOH
or (Ph3P)2PdOAc2 (5 mol %)
DCE

1. MeI (excess)
2. Ag2O, H2O
O 3. heat NH2 O
N Me N
NH2
O O
H2NNH2,
EtOH

H O O
Me N
Me N

Cp2LnNMe2 (1 mol %)
THF NH2, Ni, H2, EtOH
or (Ph3P)2PdOAc2 (5 mol %)
DCE

1. MeI (excess)
2. Ag2O, H2O
O 3. heat NH2 O
N Me N
NH2
O O
H2NNH2,
EtOH

7 Prepared by Dr. Maria Yermolina

 CHEM 234 • Organic Chemistry II • Fall 2020
Discussion activity Week 11 • Amines • KEY

Me

Ph
1.BH3•THF, or 9BBN, THF
Br
2. NaOH, H2O2
Pd(PPh3)4 (5 mol %) 3. Swern, TEMPO
KOt-Bu, PhMe PCC or PDC oxidation
Me

H
N
H N H2NHNPh
N
CHO
H
xylenes, heat
Ph cat. H+, MeOH
Ph

O OMe
Me
NH2
Me

H3O+, heat
or
H2, Pd/C, ROH 1. KOH, H2O
2. H3O+

OH O O
heat
Me
N2 NH3
Me NaNO2, HCl
Me Cl

Me

8 Prepared by Dr. Maria Yermolina