Introduction to Bioorganic Chemistry and Chemical Biology
Answers to Chapter 7
(in-text & asterisked problems)
Answer 7.1
O
HO
sulfotransferase
OR'
O
HO
NHAc
OR
O O
S
-O
O
OR'
O
S O OR
-O
O
deacetylase
NHAc
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
HO
and/or
O
OR'
HO
O
HO
NH3+
HO
NHAc
OR'
OR
OR
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Answer
7.2
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OH
HO
O
HOO
H
OH
OH
O
HO
HO
HO
O
H
OH
OH
β-D-galactose
β-D-xylose
OH
OH
O
O
OH
OH
HO
OR
α-L-fucose
α-D-mannose
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Answer
7.3
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(S)
O
HO
HO
HO (R)
O
OH
OH
(R)
OH
CO2H
HO
HO
H
OH
CO2H
HO
HO
OH
OH
L-arabinose
O
OH
D-sugar
D-sugar
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Answer
7.4
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A
Th
Compounds with the strongest axial donor lone pair would exhibit the strongest
preference for an axial OR group.
NH
>
O
OR
B
N-
>
OR
>
OR
OR
N H
>
H
N
OR
Has the strongest donor lone
pair. Note: this species would
be unstable toward SN1
>
OR
H
+N
H
OR
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Answer
7.5
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In lubiprostone, the CF2 group should favor the cyclic hemiketal relative to the parent
compound with CH2.
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1
2
Introduction to Bioorganic Chemistry and Chemical Biology: Answers to Chapter 7
Answer 7.6
The trend of faster hydrolysis of α-glucopyranosides holds for a wide range of glycosidic
derivatives. Oddly, methyl α-d-glycosides (such as gluco, galacto, and xylo) hydrolyze
more slowly than the corresponding β-anomers.
O
HO
OPh
HO
OH
OPh
O
HO
HO
OH
OH
OH
β
α
HO
HOO
H
O
HO
antibonding
orbital
..
O
HO
HOO
H
+
OPh
H
HO
+OPh
H
faster hydrolysis
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
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Answer
7.7
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retaining
HO
HOO
H
O
O
H
O
..
OR
HO
-O
HO
HOO
H
O
O
O-
O
H
+
OR
HO ..
-O
HO
HOO
H
O
O-
O
H
:O
HO
O
O
HO
HO
O
H
H
O
O
OH
HO
inverting
HO
HOO
H
O
O
H
O
..
OR
HO
HOO
H
HO
O
O-
O
H
+
OR
HO
O
H
Th
-O
O
O
HO
HOO
H
H
-O
OH
O
O
H
O
O
R
HO
OH
O
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Answer
7.8
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OH
HO
B
..
H
B
O
OR'
O
HO
O
OH
HO
H
O
H AcHN
O
UDP•Mg
H
B
R
O
..
HO
O
HO
O
H
H AcHN
O
UDP•Mg
R
O
HO
O
HOO
H
sp2
H AcHN
O
UDP•Mg
HO
O
O
O
H AcHN
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‡
H
H
OH
HO
O
O
OH
OR'
Introduction to Bioorganic Chemistry and Chemical Biology: Answers to Chapter 7
Answer 7.9
A
B
HO
HO
HO
HO
O
2
HO
O
βO
O
α
HO
O
3
β O
NHAc
6
HO
HO
O
3
HO
HO
HO
β O
OH
R
HO
HO
HO
6
4
3
OH
O
5
1
2
6
β O
HO
O
5
4
OH
3
1
2
β
O
5
4
3
1
2
α
O
O
O
NH
NHAc
OH
OH
Galβ1–4GlcNAcβ1–2Manα–Ser
Fucα1–2Galβ1–3GlcNAcβ1–3Galβ–OR
Introduction to Bioorganic Chemistry and Chemical Biology | A7151
Answer
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OH
O-
HOO
H
O
OH
HO
OH
HO
O
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
O
O
O
NH H
O
O
O
O
OH
O
OH
O
O
O
O
OH H
O
NH
OH
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Answer
7.11
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This is simply an electrophilic aromatic substitution reaction.
HO
O
HO
HO
OP OR R
O
O
HO
H
O
R
+
HO
N
H
OH
-A:
N
OH H
HO
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Answer
7.12
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The fucosyl, galactosyl, and sialyl subunits will generate at least one free aldehyde that
is still attached to the IgG.
HO
α-D-sialyl
HO
H
R'O
Th
O
R
CO2H
O
O
O
OR
NaIO4
O
RO
O
OH
HO
OR
O
NaIO4
OH
O
OH
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OR
OH
O
OH
O
H
OR
OH
O
O
O
HN
detached
OH
HO
β-L-fucosyl
O
HO
NaIO4
HO
HN
O
6-glycosyl-β-D-galactosyl
O
OH
R
CO2H
3
4
Introduction to Bioorganic Chemistry and Chemical Biology: Answers to Chapter 7
Answer 7.13
HO
O
HO
: NH2
Lys
O
HO
O
: NH
OH OH O
+ H
OH OH O
O
OH OH OH
OH OH
O
: NH
Lys
NHAc
OH OH
OH OH
CO2 +
NH
Lys
NHAc
O
or
: NH
Lys
NHAc
OH OH
NH
Lys
B:
HO
O
+
NH
Lys
H
Lys
HO
O
OH2+
Molecular modeling suggests that the
carboxylic acid of pyruvic acid
protonates the aldehyde carbonyl.
OH O
: OH2
CO2H
OH OH
NHAc
-O
O
HOO
H
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
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Answer
7.14
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-O
O
O
HOO
H
O
OH
O
GlcAβ−ibuprofen
-O
O
O
HOO
H
O
OH
O
GlcAβ(1-3)−morphine
O
O
OH
OMe
N
O
GlcAβ−naproxen
H
HO
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Answer
7.15
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Ar
OR
O
O
Ph
O
OO
t-BuPh2Si
Me
S:
Ar
+
O
O
O
O
t-BuPh2Si O
Ph
Ar
O
O
Ph
O
OO
t-BuPh2Si
O
Ph
O
t-BuPh2Si O
S
Me + Me
H3C OTf
H2O
H
O
O
O
O
t-BuPh2Si O
Ph
OR
OR
..
Ar
..
O
O O R
+
OR
Ph
O
OO
Bn
Th
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Answer
7.16
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Bn
O
O
O
H
:B
O
OO
Bn
O OO O
Bn
O
O F C S O S CF
3
3
O
O:
O
Ph
O
OO
Bn
Bn
O
O
O+
O
OO
Bn
Bn
O
O
O
O
Ph
O
Ph
:
O
Ph
O
OO
Bn
Bn
O
O
: OTf
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Tf
O
Ph
+
O
O
OO
Bn
Bn HOR
..
O
O
OTf
Ph
O
OO
Bn
Bn
O
O
OR
Introduction to Bioorganic Chemistry and Chemical Biology: Answers to Chapter 7
Answer 7.17
OBn
BnO
OBn
BnO
O
FmocO
O
PivO
OBn
BnO
-OTf
O
OBu
OBu
O+
FmocO
P OBu Me
P OBu
O
O
Me Si OTf
..
.. O SiMe
3
t-Bu
O
Me not SN
O
FmocO
O
t-Bu
2
O
FmocO
OBn
BnO
OBn
OBn
BnO
O
O
+
t-Bu
..
HO
O
Bn
O
OBn
O
FmocO
OR
O
O
Bn
PivO
PivO
O+
O
OR
PivO
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
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Answer
7.18
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NH
.. 2
N
O
..
OH+ H NNH +
2
3
O
OR
N
NH + HOR
O
OR
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Answer
7.19
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H
Fucα1 2Galβ1 4GlcNAcβ1 3Galβ1 4GlcNAcβ
Galβ1 3
B
Fucα1 2
Galβ1 4GlcNAcβ1 3Galβ1 4GlcNAcβ
GalNAcβ1 3
A
Galβ1 4GlcNAcβ1 3Galβ1 4GlcNAcβ
Fucα1 2
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Answer
7.20
HO
.. H A
O
OH
HO
HO
OH
H2NR
..
+
H
O
OH
HO
HO
OH
HO
OH
OH
H
O:
HO
H
+
H NHR
O
OH
HO
OH
OH
H : NHR
O
OH2 +
OH
OH
..
HO
Th
HO
HO
OH
OH
H
O
+
HO
+
NHR
OH
OH
: A-
H
O
+
HO
NHR
HO
OH
O
HO
HO
OH
NHR
OH
OH
OH
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Answer
7.21
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+
NHR
H
O
OH
HO
HO
H
: A-
HO
H
O
HO
NHR
H A
OH
:
HO
HO
H
O
HO
HO
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OH
H
N
R
O H
+
HO
: A-
H
O
HO
H
N
O
OH
R
5
6
Introduction to Bioorganic Chemistry and Chemical Biology: Answers to Chapter 7
Answer 7.22
B:
H
O
O
HO
HO
O
HO
OH
HO
-
OH
HO
OH
OH
O:
HO
O
H
OH
OH
HO
HO
OH
OH
O
H
O
.. -
O
H
HO
OH
OH
HO
O
..
OH
OH
..
HO
H
B
:B
HO
OH
O
HO
O
HO
OH
OH
OH
OH
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7.23
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©*Answer
B:
H
O
HO
HO
OH
O
.. -
HO
OH
O
.. -
HO
OH
OH
HO
OH
O
HO
OH
OH
B
O H
OH
OH
HO
..
HO
O
H
HO
OH
OH O
.. -
HO
O
HO
sh is
ar stu
ed d
vi y re
aC s
o
ou urc
rs e
eH w
er as
o.
co
m
O
:B
O
HO
..
O-
HO
O
OH
HO
O
H B+
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*Answer 7.24
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OH
EtO 2C
S
S
CO 2Et
OH
chair with axial OH groups
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*Answer
7.26
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HO
OH
O
HO
HO
O
HO
OH
OH
O
O
O
O
O
NHAc
(CH2) 14CH3
OH
O
O
O
OH H
HN
O
O
(CH2) 12CH3
OH
Th
OH
OH
HO
OH
Introduction to Bioorganic Chemistry and Chemical Biology | A7167
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*Answer
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O
R
O
O
OH
OH
O
H
NH
O
:B
R
O
O
O
.. NH
OH
OH
O
R
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*Answer
7.32
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HO
O
O
pyruvic acid
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O
..
O
-
OH
OH
OH
+
NH
H
B H
H
H
-
O
R
O
O
OH
OH
H 2O
R
OH OH
O
OH
OH