10.

542 – Biochemical Engineering

Spring 2005

Survey of Biocatalytic Reactions

Glutamate Dehydrogenase
Natural: α-ketoglutarate → glutamate

O H2N

HO OH HO OH

O O O O

Unnatural: 2-keto-6-hydroxyhexanoic acid → L-6-hydroxynorleucine

O H2N

OH OH
HO HO

O O

Leucine Dehydrogenase
Natural: 2-keto-4-methyl-pentanoate → L-leucine

O H2N

OH OH

O O

Unnatural: trimethylpyruvate → L-tert-leucine

O H2N

OH OH

O O
Phenylalanine dehydrogenase
Natural: phenylpyruvate → phenylalanine

O H2N

OH OH

O O

Unnatural: 5-(1,3-dioxolan-2-yl)-2-oxopentanoic acid → 2-amino-5-(1,3-dioxolan-2-

yl)pentanoic acid

O O O H2N

OH OH
O O

O O

Lactate dehydrogenase
Natural: pyruvate → lactate

O HO

OH OH

O O

Unnatural: 2-oxo-4-phenylbutanoic acid → 2-hydroxy-4-phenylbutanoic acid

O O

OH OH

O OH

Survey of Biocatalytic Reactions, p. 2

Napthalene dioxygenase
Natural: naphthalene → naphthalene-1,2-diol

OH

OH

Unnatural: 1H-indole → 1H-indole-2,3-diol

OH

OH

N N
H H

Lipases
Natural: lipid ↔ glycerol + fatty acids (Note that these enzymes are also often used in
the reverse direction)

O R2

O O

R1

HO OH

O O

R3 Ri

O HO 3 OH

Survey of Biocatalytic Reactions, p. 3

Unnatural:

(1) 2-oxo-4-phenylazetidin-3-yl acetate → 3-hydroxy-4-phenylazetidin-2-one

O O
HN HN

O OH

(2) 1-phenylethanamine + ethyl methoxyacetate → ethyl methoxyacetate

O

O
NH2 HN

O
O

Subtilisin (protease)
Natural: peptide bond hydrolysis

O R2 O O

NH NH NH
NH OH

R1 O R3 R1

R2 O

NH
H2N

O R3

Survey of Biocatalytic Reactions, p. 4

Unnatural:
F F F
(1)
F F F

O O H + O
H

MeO N HO N MeO N

N O N O N O
OMe OMe OMe
DHP Methyl Ester R-DHP Acid S-DHP Methyl Ester

(2)

O O

S O
N
O
O O

O O

S OH
N
O
O O

Survey of Biocatalytic Reactions, p. 5

Nitrilase
Natural: acrylonitrile → acrylic acid (acrylate)

OH

N O

Unnatural: pyrazine-2-carbonitrile → pyrazine-2-carboxylic acid

N N
N OH

N N

Survey of Biocatalytic Reactions, p. 6