Enantioselective Phosphorylation Glycerol kinase [586] is not only able to
accept its natural substrate, glycerol, to form sn-glycerol-3-phosphate [587], or
close analogs of it such as dihydroxyacetone (see Scheme 2.78), but it is also able to
transform a large variety of prochiral or racemic primary alcohols into chiral
phosphates (Scheme 2.80) [588–590]. The latter compounds represent synthetic
precursors to phospholipids [591] and their analogs [592].
As depicted in Scheme 2.80, the glycerol backbone of the substrates may be
varied quite widely without affecting the high specificity of glycerol kinase. In
resolutions of racemic substrates, both the phosphorylated species produced and the
O
O
N
HN
O
OH
HO
O
-O
OH
OH
HO
O
OH
OH
HO
HO O
CO 2 H
O
O
N
H
HN
CO 2 H
O
O
N
HN
O
OH
HO
O
O
-O
OH
HO
O
PRPP = 5-phospho-D-ribosyl-α-1-pyrophosphate
= phosphate
PRPP
UMP
O-5-P
decarboxylase
pyrophosphatase
O-5-P = orotidine-5'-monophosphate
O-5-P pyrophosphorylase
PYR = pyruvate
PEP = phosphoenol pyruvate
PRPP-synthase
adenylate kinase
pyruvate kinase
pyruvate kinase
ribokinase
2 PYR
2 PEP
PYR
PEP
AMP
ATP
ADP
ATP
P
P
P
P P
O-5-P
CO 2
P
PP i
2 P i
P
Scheme 2.79 Phosphorylation of D-ribose and enzymatic synthesis of UMP
H
OH
X
R
OH
X
R
H
OH
X
R
= phosphate
rac
+
glycerol kinase
P
P
pyruvate kinase
ADP
ATP
pyruvate
phosphoenol pyruvate
R
X
e.e. Phosphate [%]
e.e. Alcohol [%]
Cl
O
>94
88
SH
O
94
n.d.
CH 3 O
O
9 0
n . d .
Br
O
90
n.d.
OH
NH
>94
94
Scheme 2.80 Enantioselective phosphorylation of glycerol derivatives
2.1 Hydrolytic Reactions
111