4.1.1.7: benzoylformate decarboxylase

691020, 747071

(p-methoxybenzoyl)formate

p-methoxybenzaldehyde + CO2

4800

(p-methylbenzoyl)formate

p-methylbenzaldehyde + CO2

(R)-2-hydroxy-1-phenylpropanone + acetaldehyde

(S)-2-hydroxy-1-phenylpropanone + acetaldehyde

2 benzaldehyde

(R)-benzoin

4 entries

2-fluoro-benzaldehyde + acetaldehyde

(S)-1-(2-fluoro-phenyl)-2-hydroxy-propan-1-one

2-fluoro-benzaldehyde + acetaldehyde

1-(2-fluoro-phenyl)-2-hydroxy-propan-1-one

91% enantiomeric excess of the (S)-2-hydroxypropanone derivative

2-fluorobenzaldehyde

(R)-1,2-Bis-(2-fluoro-phenyl)-2-hydroxy-ethanone

carboligation

68% yield and more than 99% enantiomeric excess of the (R)-enantiomer

2-furaldehyde

(R)-1,2-di-furan-2-yl-2-hydroxy-ethanone

carboligation

62% yield and 94% enantiomeric excess of the (R)-enantiomer

2-furaldehyde + acetaldehyde

(S)-1-Furan-2-yl-2-hydroxy-propan-1-one

2-ketohexanoate

valeraldehyde + CO2

702341

2-ketopentanoate

butyraldehyde + CO2

702341

2-methyl-benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-(2-methylphenyl)-propanone

2-methyl-benzaldehyde + acetaldehyde

2-hydroxy-1-o-tolyl-propan-1-one

4% enantiomeric excess of the (S)-2-hydroxypropanone derivative

2-oxo-3-phenylpropanoic acid

phenylacetaldehyde + CO2

2-oxo-4-methylhexanoic acid

3-methylpentanal + CO2

2-oxo-4-methylpentanoic acid

3-methylbutanal + CO2

2-oxo-4-phenylbutanoic acid

3-phenylpropionaldehyde + CO2

2-oxo-5-phenylpentanoic acid

4-phenylpentanal + CO2

2-oxobutanoate

propionaldehyde + CO2

702341, 747471

2-oxobutanoic acid

propionaldehyde + CO2

2-oxohexanoate

valeraldehyde + CO2

2-oxohexanoic acid

valeraldehyde + CO2

2-oxopentanoate

butyraldehyde + CO2

2-oxopentanoic acid

butyraldehyde + CO2

3 benzaldehyde + acetaldehyde

(R)-benzoin + (S)-2-hydroxypropiophenone

3,5-Difluoro-benzaldehyde + acetaldehyde

(S)-1-(3,5-Difluoro-phenyl)-2-hydroxy-propan-1-one

3,5-dimethoxybenzaldehyde + acetaldehyde

(S)-1-(3,5-Dimethoxy-phenyl)-2-hydroxy-propan-1-one

3-Benzyloxy-benzaldehyde + acetaldehyde

1-(3-Benzyloxy-phenyl)-2-hydroxy-propan-1-one

more than 99% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-bromo-benzaldehyde + acetaldehyde

(S)-1-(3-bromo-phenyl)-2-hydroxy-propan-1-one

3-bromo-benzaldehyde + acetaldehyde

1-(3-bromo-phenyl)-2-hydroxy-propan-1-one

96% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-chloro-benzaldehyde + acetaldehyde

(S)-1-(3-chloro-phenyl)-2-hydroxy-propan-1-one

3-chloro-benzaldehyde + acetaldehyde

1-(3-chloro-phenyl)-2-hydroxy-propan-1-one

94% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-ethoxy-4-hydroxybenzoylformate

ethyl vanillin + CO2

3-ethoxy-benzaldehyde + acetaldehyde

(S)-1-(3-ethoxy-phenyl)-2-hydroxy-propan-1-one

3-ethoxy-benzaldehyde + acetaldehyde

1-(3-ethoxy-phenyl)-2-hydroxy-propan-1-one

97% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-fluoro-benzaldehyde + acetaldehyde

(S)-1-(3-fluoro-phenyl)-2-hydroxy-propan-1-one

3-formyl-benzonitrile + acetaldehyde

3-((S)-2-hydroxy-propionyl)-benzonitrile

3-formyl-benzonitrile + acetaldehyde

3-(2-hydroxy-propionyl)-benzonitrile

92% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-hydroxy-benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-(3-hydroxy-phenyl)-propan-1-one

3-hydroxy-benzaldehyde + acetaldehyde

2-hydroxy-1-(3-hydroxy-phenyl)-propan-1-one

92% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-isopropoxy-benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-(3-isopropoxy-phenyl)-propan-1-one

3-isopropoxy-benzaldehyde + acetaldehyde

2-hydroxy-1-(3-isopropoxy-phenyl)-propan-1-one

more thahn 99% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-methoxy-benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-(3-methoxy-phenyl)-propan-1-one

3-methoxy-benzaldehyde + acetaldehyde

2-hydroxy-1-(3-methoxy-phenyl)-propan-1-one

96% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-methoxybenzaldehyde

(R)-2-Hydroxy-1,2-bis-(3-methoxy-phenyl)-ethanone

carboligation

18% yield and more than 99% enantiomeric excess of the (R)-enantiomer

3-Methoxymethoxy-benzaldehyde + acetaldehyde

(S)-2-Hydroxy-1-(3-methoxymethoxy-phenyl)-propan-1-one

3-methyl-2-oxobutanoate

2-methylpropanal + CO2

3-methyl-2-oxobutanoic acid

2-methylpropanal + CO2

3-methyl-2-oxopentanoate

2-methylbutanal + CO2

3-methyl-2-oxopentanoic acid

2-methylbutanal + CO2

3-methyl-benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-m-tolyl-propan-1-one

3-methyl-benzaldehyde + acetaldehyde

2-hydroxy-1-m-tolyl-propan-1-one

97% enantiomeric excess of the (S)-2-hydroxypropanone derivative

3-Phenoxy-benzaldehyde + acetaldehyde

2-Hydroxy-1-(3-phenoxy-phenyl)-propan-1-one

more than 99% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4,4-dimethyl-2-oxopentanoic acid

3,3-dimethylbutanal + CO2

4-Bromo-benzaldehyde + acetaldehyde

1-(4-Bromo-phenyl)-2-hydroxy-propan-1-one

83% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-bromobenzaldehyde

(R)-1,2-bis-(4-bromo-phenyl)-2-hydroxy-ethanone

carboligation

13% yield and more than 99% enantiomeric excess of the (R)-enantiomer

4-bromobenzaldehyde + acetaldehyde

(S)-1-(4-Bromo-phenyl)-2-hydroxy-propan-1-one

4-Chloro-benzaldehyde + acetaldehyde

1-(4-Chloro-phenyl)-2-hydroxy-propan-1-one

82% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-chlorobenzaldehyde

(R)-1,2-bis-(4-chloro-phenyl)-2-hydroxy-ethanone

carboligation

17% yield and more than 99% enantiomeric excess of the (R)-enantiomer

4-chlorobenzaldehyde + acetaldehyde

(S)-1-(4-Chloro-phenyl)-2-hydroxy-propan-1-one

4-fluoro-benzaldehyde + acetaldehyde

(S)-1-(4-fluoro-phenyl)-2-hydroxy-propan-1-one

4-fluoro-benzaldehyde + acetaldehyde

1-(4-fluoro-phenyl)-2-hydroxy-propan-1-one

87% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-fluorobenzaldehyde

(R)-1,2-Bis-(4-fluoro-phenyl)-2-hydroxy-ethanone

carboligation

25% yield and more than 99% enantiomeric excess of the (R)-enantiomer

4-Formyl-benzonitrile + acetaldehyde

4-(2-Hydroxy-propionyl)-benzonitrile

74% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-formylbenzonitrile + acetaldehyde

4-((S)-2-Hydroxy-propionyl)-benzonitrile

4-Hydroxy-benzaldehyde + acetaldehyde

2-Hydroxy-1-(4-hydroxy-phenyl)-propan-1-one

86% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-hydroxybenzaldehyde + acetaldehyde

(S)-2-Hydroxy-1-(4-hydroxy-phenyl)-propan-1-one

4-Methoxy-benzaldehyde + acetaldehyde

2-Hydroxy-1-(4-methoxy-phenyl)-propan-1-one

92% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-methoxybenzaldehyde

(R)-2-Hydroxy-1,2-bis-(4-methoxy-phenyl)-ethanone

carboligation

12% yield and more than 99% enantiomeric excess of the (R)-enantiomer

4-methoxybenzaldehyde + acetaldehyde

(S)-2-Hydroxy-1-(4-methoxy-phenyl)-propan-1-one

4-methyl-2-oxopentanoate

3-methylbutanal + CO2

4-Methyl-benzaldehyde + acetaldehyde

2-Hydroxy-1-p-tolyl-propan-1-one

88% enantiomeric excess of the (S)-2-hydroxypropanone derivative

4-methylbenzaldehyde

(R)-2-Hydroxy-1,2-di-p-tolyl-ethanone

carboligation

69% yield and more than 99% enantiomeric excess of the (R)-enantiomer

4-methylbenzaldehyde + acetaldehyde

(S)-2-Hydroxy-1-p-tolyl-propan-1-one

4-methylthio-2-oxobutanoate

3-(methylsulfanyl)propanal + CO2

5-Isopropyl-furan-2-carbaldehyde + acetaldehyde

2-Hydroxy-1-(5-isopropyl-furan-2-yl)-propan-1-one

73% enantiomeric excess of the (S)-2-hydroxypropanone derivative

5-methyl-furan-2-carbaldehyde

(R)-2-Hydroxy-1,2-bis-(5-methyl-furan-2-yl)-ethanone

carboligation

50% yield and 96% enantiomeric excess of the (R)-enantiomer

5-Methyl-furan-2-carbaldehyde + acetaldehyde

2-Hydroxy-1-(5-methyl-furan-2-yl)-propan-1-one

86% enantiomeric excess of the (S)-2-hydroxypropanone derivative

8-Hydroxy-quinoline-2-carbaldehyde + acetaldehyde

2-Hydroxy-1-(8-hydroxy-quinolin-2-yl)-propan-1-one

acetaldehyde

(R)-acetoin

acetaldehyde + acetaldehyde

(3R)-3-hydroxybutan-2-one

acetic acid 3-formyl-phenyl ester + acetaldehyde

(S)-1-(3-acetoxyphenyl)-2-hydroxy-propanone

acetic acid 3-formyl-phenyl ester + acetaldehyde

acetic acid 3-(2-hydroxy-propionyl)-phenyl ester

more than 99% enantiomeric excess of the (S)-2-hydroxypropanone derivative

benzaldehyde + acetaldehyde

(R)-2-hydroxypropiophenone

reactions performed at high benzaldehyde concentrations and at high hydrostatic pressures show an increase in (R)-2-hydroxypropiophenone ((R)-2-HPP) formation catalyzed by BFD variants F464I, A460I, and A460I/F464I. For BFD mutant A460I/F464I there is an increase in the ee of (R)-2-HPP up to 80%, whereas at atmospheric conditions this variant synthesizes (R)-2-HPP with an ee of only 50%. Alkaline conditions (up to pH 8.5) and high hydrostatic pressures result in an increase of (R)-2-HPP synthesis, especially in the case of variant A460I and F464I

715697

benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-phenyl-propanone

benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-phenylpropan-1-one

691794

benzaldehyde + acetaldehyde

(S)-2-hydroxy-1-phenylpropanone

benzaldehyde + acetaldehyde

(S)-2-hydroxypropiophenone

benzaldehyde + acetaldehyde

2-hydroxy-1-phenyl-propan-1-one

92% enantiomeric excess of the (S)-2-hydroxypropanone derivative

benzaldehyde + acetaldehyde

2-hydroxypropiophenone

benzaldehyde + benzaldehyde

(2R)-2-hydroxy-1,2-diphenylethanone

benzaldehyde + benzaldehyde

(R)-benzoin

5 entries

benzoin + acetaldehyde

2-hydroxy-1-phenylpropanone

Benzoylformate

11 entries

benzoylformate

benzaldehyde + CO2

40 entries

Benzoylformate + acetaldehyde

(S)-2-Hydroxypropiophenone

benzylformate

benzaldehyde + CO2

butyraldehyde

cyclohex-1-ene-1-carbaldehyde + acetaldehyde

(S)-1-Cyclohex-1-enyl-2-hydroxy-propan-1-one

Cyclohex-1-enecarbaldehyde + acetaldehyde

1-Cyclohex-1-enyl-2-hydroxy-propan-1-one

94% enantiomeric excess of the (S)-2-hydroxypropanone derivative

cyclohexanecarbaldehyde + acetaldehyde

(S)-1-cyclohexyl-2-hydroxy-propan-1-one

cyclohexanecarbaldehyde + acetaldehyde

1-cyclohexyl-2-hydroxy-propan-1-one

61% enantiomeric excess of the (S)-2-hydroxypropanone derivative

Furan-2-carbaldehyde + acetaldehyde

1-Furan-2-yl-2-hydroxy-propan-1-one

45% enantiomeric excess of the (S)-2-hydroxypropanone derivative

isovaleraldehyde

(R)-5-hydroxy-2,7-dimethyloctan-4-one

m-bromo-benzoylformate

m-bromo-benzaldehyde + CO2

wild-type enzyme: 68% conversion with 96% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 97% conversion with more than 98% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 98.5% enantiomeric excess of the (S)-2-hydroxy ketone

m-chloro-benzoylformate

m-chloro-benzaldehyde + CO2

wild-type enzyme: 94% conversion with 94% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 97% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 98% enantiomeric excess of the (S)-2-hydroxy ketone

m-fluoro-benzoylformate

m-fluoro-benzaldehyde + CO2

wild-type enzyme: 100% conversion with 87% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 94% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone

m-methoxy-benzoylformate

m-methoxy-benzaldehyde + CO2

wild-type enzyme: 94% conversion with 96% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 99% enantiomeric excess of the (S)-2-hydroxy ketone

m-methyl-benzoylformate

m-methyl-benzaldehyde + CO2

wild-type enzyme: 99% conversion with 97% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 99% enantiomeric excess of the (S)-2-hydroxy ketone

methyl benzoylphosphonate

702289

n-butanal

(R)-5-hydroxyoctan-4-one

n-pentanal

(R)-6-hydroxydecan-5-one

Naphthalene-2-carbaldehyde + acetaldehyde

2-Hydroxy-1-naphthalen-2-yl-propan-1-one

nicotinaldehyde + acetaldehyde

(S)-2-Hydroxy-1-pyridin-3-yl-propan-1-one

o-bromo-benzoylformate

o-bromo-benzaldehyde + CO2

wild-type enzyme: no activity, mutant enzyme L476Q: 98% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 90% conversion with 99% enantiomeric excess of the (S)-2-hydroxy ketone

o-chloro-benzoylformate

o-chloro-benzaldehyde + CO2

wild-type enzyme: no activity, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 85% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone

o-fluoro-benzoylformate

o-fluoro-benzaldehyde + CO2

wild-type enzyme: 91% conversion with 89% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 83% conversion with 98% enantiomeric excess of the (S)-2-hydroxy ketone

o-methoxy-benzoylformate

o-methoxy-benzaldehyde + CO2

wild-type enzyme: no conversion, mutant enzyme L476Q: 97% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 46% conversion with 99% enantiomeric excess of the (S)-2-hydroxy ketone

o-methyl-benzoylformate

o-methyl-benzaldehyde + CO2

wild-type enzyme: 4% conversion, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 83% conversion with 98% enantiomeric excess of the (S)-2-hydroxy ketone

o-methylbenzaldehyde + acetaldehyde

(2S)-2-hydroxy-1-(2-methylphenyl)propan-1-one

mutant enzyme L476Q and M365L/L461S selectively catalyzes the formation of enantiopure (S)-2-hydroxy-1-(2-methylphenyl)propan-1-one with excellent yield, a reaction which is only poorly catalyzed by the wild-type enzyme

p-bromo-benzoylformate

p-bromo-benzaldehyde + CO2

wild-type enzyme: 42% conversion with 83% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with 96.5% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 96% enantiomeric excess of the (S)-2-hydroxy ketone

p-chloro-benzoylformate

p-chloro-benzaldehyde + CO2

wild-type enzyme: 85% conversion with 82% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 96.5% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 100% conversion with 95.5% enantiomeric excess of the (S)-2-hydroxy ketone

p-fluoro-benzoylformate

p-fluoro-benzaldehyde + CO2

wild-type enzyme: 69% conversion with 87% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with 97% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 87% conversion with 97% enantiomeric excess of the (S)-2-hydroxy ketone

p-methoxy-benzoylformate

p-methoxy-benzaldehyde + CO2

wild-type enzyme: 23% conversion with 92% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 99% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 67% conversion with 42% enantiomeric excess of the (S)-2-hydroxy ketone

p-methyl-benzoylformate

p-methyl-benzaldehyde + CO2

wild-type enzyme: 65% conversion with 88% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme L476Q: 100% conversion with more than 98% enantiomeric excess of the (S)-2-hydroxy ketone, mutant enzyme M365L-L461S: 98% conversion with 98% enantiomeric excess of the (S)-2-hydroxy ketone

p-nitro-benzoylformate

very poor substrate

702290

p-nitrobenzoylformate

p-nitrobenzaldehyde + CO2

678577

phenylglyoxylate

benzaldehyde + CO2

4 entries

Phenylpyruvate

Phenylacetaldehyde + CO2

propanal

4-hydroxyhexan-3-one

propionaldehyde

pyridine-2-carbaldehyde

(R)-2-Hydroxy-1,2-di-pyridin-2-yl-ethanone

carboligation

70% yield and 94% enantiomeric excess of the (R)-enantiomer

Pyridine-2-carbaldehyde + acetaldehyde

2-Hydroxy-1-pyridin-2-yl-propan-1-one

Pyridine-3-carbaldehyde + acetaldehyde

2-Hydroxy-1-pyridin-3-yl-propan-1-one

pyruvate

acetaldehyde + CO2

Quinoline-4-carbaldehyde + acetaldehyde

2-Hydroxy-1-quinolin-4-yl-propan-1-one

thiophene-2-carbaldehyde

(S)-2-Hydroxy-1,2-di-thiophen-2-yl-ethanone

carboligation

65% yield and 95% enantiomeric excess of the (R)-enantiomer

thiophene-2-carbaldehyde + acetaldehyde

(S)-2-hydroxy-1-thiophen-2-yl-propan-1-one

thiophene-2-carbaldehyde + acetaldehyde

2-hydroxy-1-thiophen-2-yl-propan-1-one

83% enantiomeric excess of the (S)-2-hydroxypropanone derivative

[m-(Fluoromethyl)benzoyl]formate

4800

[p-(Chloromethyl)benzoyl]formate

4799, 4800

[p-(Fluoromethyl)benzoyl]formate