Chapter 11
Biological Aspects of Metal
Enolates
Li-June Ming
Department of
Chemistry and Institute for Biomolecular Science
Tampa, Florida 33620-5250
To
my mom and Shu-Ching
for their endless love and support throughout
my career
I. ABBREVIATIONS
II. INTRODUCTION
A. Scope of the Chapter
B. Enol-containing Natural Products
C.
Enols and Enolates in Chemical Reactions
D. Stabilization of the Enol
Functional Group in Biological Processes
III. Metal Enolates in Biological Systems
A. Metal
Complexes of Enolates
B. Enol-containing
Biochemicals and Pharmaceuticals and Their Metal Complexes
1. Biochemicals
a. Ascorbic acid
b. Flavonoids
c. Mimosine and analogues
d. Kojic
acid and pyranones
e. Furanones
f. Quinone derivatives
g. Tropolones
2. Pharmaceuticals
a. Antibiotic
tetracyclines
b. Oxicam anti-inflammatory
drugs
c. Deferiprone for iron
overload
d. Antimalarial hydroxynaphthoquinones
and analogues
3. Miscellaneous applications
of metal enolates
a. Antitumor agents
b. Biosensors and
imaging agents
IV. METALLOENOLATES AND
ASSOCIATED ENZYMES
A. Enols and Associated
Enzymes in Glycolysis and Other Sugar Metabolisms
1.
Enols in ketose–aldose isomerization
2. Stabilization of enol intermediates in aldolases
and epimerases
3. Enolates in triosephosphate isomerase
4. Role of metal ions in enolases and the enolase superfamily
5. Metal–enolate interaction in pyruvate kinase
B. Rubisco
C. Ascorbic Acid Biosynthesis and Biological Roles
D. Amine Oxidases
E. Quercetin 2,5-Dioxygenase
F. Acireductone Dioxygenase
G.
b-Diketone-cleaving
Enzymes
1.
Hydrolytic cleavage
2.
Oxidative cleavage
H. TetA and Tetracycline Resistance
I. Enols in Enzyme Inhibition
V. REFERENCES