Selective Activation of C?H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis

Article abstract of DOI:10.1002/anie.201708668

Selective oxyfunctionalizations of inert C?H bonds can be achieved under mild conditions by using peroxygenases. This approach, however, suffers from the poor robustness of these enzymes in the presence of hydrogen peroxide as the stoichiometric oxidant. Herein, we demonstrate that inorganic photocatalysts such as gold–titanium dioxide efficiently provide H₂O₂ through the methanol-driven reductive activation of ambient oxygen in amounts that ensure that the enzyme remains highly active and stable. Using this approach, the stereoselective hydroxylation of ethylbenzene to (R)-1-phenylethanol was achieved with high enantioselectivity (>98 % ee) and excellent turnover numbers for the biocatalyst (>71 000).

Full text of DOI:10.1002/anie.201708668

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Accepted Article
Title: Selective activation of C-H bonds by cascading photochemistry
with biocatalysis
Authors: Wuyuan Zhang, Bastien O. Burek, Elena Fernández-Fueyo,
Miguel Alcalde, Jonathan Z. Bloh, and Frank Hollmann
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201708668
Angew. Chem. 10.1002/ange.201708668
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Selective activation of C-H bonds by cascading photochemistry
with biocatalysis
†
†
*
Wuyuan Zhang , Bastien O. Burek , Elena Fernández-Fueyo, Miguel Alcalde, Jonathan Z. Bloh , and
*
Frank Hollmann
Abstract: Selective oxyfunctionalisation of inert C-H bonds under
mild conditions can be achieved using peroxygenases. This
approach, however, is impaired by the poor robustness of these
enzymes in the presence of hydrogen peroxide as the stoichiometric
oxidant. Here, we demonstrate that inorganic photocatalysts such as
system (glucose is oxidised only once to the corresponding
lactone generating one equivalent of H ) together the pH shift
originating from gluconic acid accumulation pose significant
technological challenges to this approach (especially if used at
preparative scale, Table S5 for further details). Therefore, we
recently reported an enzymatic cascade to fully oxidise methanol
2
O
2
2 2
gold-titanium dioxide efficiently provide H O from methanol-driven
reductive activation of ambient oxygen in suitable amounts to ensure
high reactivity and robustness of the enzyme. Using this approach
stereoselective hydroxylation of ethyl benzene to (R)-1-phenyl
ethanol in high enantioselectivity (>98% ee) and excellent turnover
numbers of the biocatalyst (>71.000) was achieved.
to CO
2 2 2
and utilise the reduction equivalents liberated for H O
[
3]
generation to promote peroxygenase reactions (Scheme 1).
For this, a rather complicated cascade comprising four enzymes
and one cofactor was established. Despite the success of this
reaction system, we asked ourselves whether a simpler and
more elegant in situ H
Inspired by recent work by Choi and Tada, we set out to
evaluate gold-loaded TiO (Au-TiO ) as plasmonic photocatalyst
for the oxidation of methanol coupled to reductive activation of
molecular oxygen to promote peroxygenase-catalysed
oxyfunctionalisation reactions (Scheme 1).
2 2
O generation method is possible.
[
4]
Selective oxyfunctionalisation of (non-)activated C-H bonds still
represents one of the major challenges in organic synthesis.
Heme-dependendent oxygenases are valuable catalysts for this
task as they confine highly reactive Fe(IV)O species in the
2
2
[
1]
sterically well-defined active site of an enzyme. Today, mostly
P450 monooxygenases are considered as biocatalysts but
peroxygenases (E.C.1.11.2.1) represent a practical alternative
especially due to their ease of application. Instead of relying on
complex electron supply chains providing the enzymes with
reducing equivalents as in case of P450 monooxygenases,
peroxygenases use hydrogen peroxide (H
the catalytically active oxyferryl species (Compound I).
, however, also is a potent inactivator of heme-enzymes
via oxidative decomposition of the prosthetic group. Therefore,
in situ generation of H in low concentrations is the preferred
approach to alleviate this challenge.
achieved through in situ reduction of O
2 2
O ) directly to form
[
2]
2 2
H O
2
O
2
[
1b]
Generally, this is
to H , posing the
2
2 2
O
question about the nature of the electron donor used for this
reaction. Next to electrochemical methods, oxidation of
stoichiometric cosubstrates such as EDTA, amino acids,
2 2
Scheme 1. Comparison of the previously reported in situ H O generation to
promote peroxygenase-catalysed hydroxylation of alkanes using the
recombinant peroxygenase from Agrocybe aegerita (rAaeUPO). Upper: the
previously reported multi-enzyme cascade comprising alcohol oxidase (AOx),
formaldehyde dismutase (FDM), formate dehydrogenase (FDH), 3-hydroxy
benzoate-6-hydroxylase (3HB6H) as well as the nicotinamide cofactor
[
1b]
alcohols and other reductants have been investigated. Today,
the most common system for in situ generation of H certainly
2
O
2
is glucose/glucose oxidase. The poor atom efficiency of this
+ [3]
(
NADH/NAD ); lower: photochemical oxidation of methanol using Au-loaded
TiO (Au-TiO ).
2
2
†
[*]
Dr. W. Zhang , Prof. Dr. F. Hollmann
Department of Biotechnology
Delft University of technology
To test our hypothesis, we synthesised Au-loaded TiO
2
[
5]
Van der Maasweg 9, 2629HZ Delft (The Netherlands)
E-mail: f.hollmann@tudelft.nl
(
rutile phase) as methanol oxidation catalyst (SI for details)
and used it for the selective hydroxylation of ethyl benzene to
R)-1-phenyl ethanol catalysed by the recombinant evolved
peroxygenase from Agrocybe aegerita (rAaeUPO) as model
†
B. O. Burek , Dr. J. Z. Bloh
(
DECHEMA-Forschungsinstitut
Theodor-Heuss-Allee 25, 60486 Frankfurt am Main (Germany)
E-mail: bloh@dechema.de
Dr. E. Fernández-Fueyo
Centro de Investigaciones Biológicas , CSIC, Madrid (Spain)
Prof. Dr. M. Alcalde
[
6]
reaction.
Pleasingly, the proof-of-concept reaction proceeded
smoothly to full conversion (Figure 1). Overall 10.7 mM of (R)-1-
Department of Biocatalysis,
Institute of Catalysis, CSIC
phenylethanol (98.2
corresponding to a turnover number (TN=molproduct  molcatalyst
of more than 71.000 for the biocatalyst. The sole by-product
detectable was traces of acetophenone originating from the
over-oxidation of the product by rAaeUPO (commencing upon
%
ee) was obtained within 72
h
)
-
1
28049 Madrid (Spain)
†
[
]
Both authors contributed equally.
Supporting information for this article is given via a link at the end of
the document.
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Angewandte Chemie International Edition
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COMMUNICATION
depletion of the starting material). Omitting the biocatalyst
resulted in small amounts (<0.15 mM) of racemic 1-phenyl
ethanol. In the absence of the photocatalyst or performing the
reactions in the darkness resulted in no detectable product
formation. In the absence of methanol, some product formation
here that MeOH not only increased the overall reaction rate but
also positively influenced the robustness of the process (Figure
S 31 and Table S3).
In terms of photocatalyst concentration there seemed to be
-1
an optimal value around approx. 10 g L with respect to the rate
of the photoenzymatic hydroxylation reaction (Table 1, entries 5,
9 and 10). This observation falls into place considering the
decreasing optical transparency of the reaction mixture with
increasing photocatalyst loading (Figure S 26). Hence, the
2
was observed, which we attribute to Au-TiO -catalysed water
oxidation (Figures S 29, 30).
2 2
increasing H O generation activity with increasing photocatalyst
concentration was counteracted by the decreasing transparency
of the reaction mixtures. Again, there was a good correlation
between the overall rate with the steady state
concentration.
2 2
H O
Increasing the enzyme concentration above 150 nM resulted
in no further increase of the overall reaction rate (Table 1,
entries 5, 7 and 8). A plausible explanation is that above this
value the system was entirely H
molecule generated was consumed productively by the
enzyme. Since the H formation rate under these conditions
was 0.52 mM h and the initial enzymatic product formation rate
2 2
O -limited, i.e. almost every
2 2
H O
2
O
2
-1
-1
2 2
was 0.45 mM h , the efficiency for the enzymatic H O utilisation
was approximately 87%. On the contrary, when the enzyme
concentration was decreased to a third, the reaction rate was
approximately halved, indicating that H
2
O
2
was no longer the
utilisation
(
sole) limiting factor. Under these conditions, the H O
2 2
efficiency dropped to 52%, as not all of the peroxide was
consumed by the enzyme anymore and the excess was
degraded by the photocatalyst and other unproductive
processes.
The photon flux inside the reaction vessel, determined using
Figure 1. Photochemoenzymatic hydroxylation of ethyl benzene to (R)-1-
phenyl ethanol combining Au-TiO as photocatalyst for in situ H generation
and rAaeUPO for the stereospecific hydroxylation reaction (). Negative
controls excluding enzyme (), light (), methanol () or rutile Au-TiO ().
Reaction conditions: [methanol] = 250 mM, [rutile Au-TiO ] = 5 mg mL ,
rAaeUPO] = 150 nM and [ethylbenzene] = 15 mM in 60 mM phosphate buffer
pH 7.0) under illumination.
[8]
-1 -1
ferrioxalate actinometry was 2851 mE L h . Consequently,
under standard conditions (150 nM UPO, 250 mM methanol) the
photonic efficiencies of hydrogen peroxide and (R)-1-phenyl
ethanol formation were 0.036% and 0.032%, respectively.
Assuming that only fraction of light corresponding to the band
gap of the rutile photocatalyst (≥3 eV / ≤413 nm, 0.7% of the
lamp intensity, Figure S 7) was responsible for the activity, a
photonic efficiency of 5.2% for hydrogen peroxide and 4.5% for
the enzymatic conversion product can be estimated, respectively.
2
2 2
O
2
-
1
2
[
(
It should be mentioned that evaporation of the reagents can
be a challenge for the current reaction setup. Especially
reactions with volatile reagents suffered from poor mass
balances if exposed to the ambient atmosphere. Optimised
setups, particularly closed vessels, circumvent this apparent
limitation (Table S 2).
Next, we systematically investigated the influence of the
single reagents on the rate of the photoenzymatic hydroxylation
reaction (Table 1, and Figures S17-25). The concentration of
MeOH had a significant effect on the initial rate steadily
increasing with [MeOH] (Table 1, entries 1-6) and correlating
well with the increasing formation rate and steady-state
In view of previously reported photonic efficiencies of only 1%
[9]
2
for TiO
this may suggest that the photocatalyst used here
could also harvest some of the visible fraction as well,
presumably via the gold plasmonic resonance at approximately
5
50-600 nm (Figure S6).
1
H
NMR analysis revealed that the Au-TiO2-catalysed
oxidation of methanol did not stop at the formaldehyde level but
also produced formic acid and, presumably, CO2 (Figures S27,
8).
2
concentrations of H
2 2 2 2 2
O . Au-TiO is known to also oxidise H O to
O
2
thereby preventing its continuous accumulation in the
[
4a, 7]
reaction mixture.
oxidation at the catalyst surface which explains the higher
steady state concentration of H in the presence of methanol.
2 2
Hence, both H O and MeOH compete for
2 2
O
Above approx. 250 mM MeOH the photocatalyst surface
appeared to be fully saturated as no further increase of the
product formation rate was observed. It is also worth mentioning
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COMMUNICATION
[
a]
2 2
Table 1. Photochemical in situ H O generation to promote peroxygenase catalysed oxyfunctionalisation reaction.
Entry
Electron [rAaeUPO] [electron
[Au-TiO
2
]
Initial rate
Steady-State [(R)-1-phenyl
GC-yield
TON
-
1
-1
[b]
[d]
donor
[nM]
donor] [mM] [g L ]
[mM h ]
[H
2 2
O ] [M]
ethanol]
[%]
(rAaeUPO)
[
c]
-3 [e]
[
mM]
10
Product
0.17
0.20
0.26
0.24
0.45
0.46
0.27
0.47
0.46
0.29
0.73
0.58
0.20
0.26
2 2
H O
1
2
3
4
5
6
7
8
9
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
HCHO
NaHCO
EtOH
150
150
150
150
150
150
50
0
5
0.37
0.56
0.28
0.56
0.52
n.d.
42
55
2.9
26
24
71
76
19
22
39
42
71
69
55
31
79
67
91
84
25
35
5
5
3.3
50
5
128
231
156
n.d.
156
156
160
97
5.9
100
250
500
250
250
250
250
250
250
250
250
5
6.4
5
10.7
10.4
2.8
>99
97
5
5
0.52
0.52
1.05
0.44
1.01
0.98
0.32
0.36
36
350
150
150
150
150
150
150
5
10.7
11.9
10.1
13.7
12.6
3.8
97
10
20
5
>99
>99
>99
99
10
11
12
13
14
[
[
[
g]
g]
h]
[g]
1050
[g]
2
5
193
154
122
5
33
i
[h]
PrOH
5
5.3
46
[
a] reaction conditions: [ethylbenzene] = 15 mM in 60 mM phosphate buffer (pH 7.0) at 30 °C for 72 hours under illumination; [b] as determined in comparative
experiments illuminating Au-TiO in the reaction buffer (Figures S11, S14, S18 and S21); n.d. = not determined. [c] Product with 98% ee was obtained unless
2
-
1
-
indicated otherwise; [d] GC-yield = [(R)-1-phenyl ethanol]final  ([(R)-1-phenyl ethanol]final + [ethyl benzene]final) ; [e] TON = [(R)-1-phenyl ethanol]final  [rAaeUPO]
1
;
[g] determined at 100 mM of the sacrificial reductant.
[
11]
To further investigate this (desired) overoxidation of
In line with the reported substrate scope of rAaeUPO a range
of (cyclo)alkanes and alkylaromatic compounds were converted
into the corresponding alcohols.
methanol, a set of experiments was conducted substituting
methanol with formaldehyde and formate, respectively, under
otherwise identical conditions (Table 1, entries 11, 12).
Formaldehyde and formate gave approximately 32% and 18%
faster reaction rates than methanol, respectively. This can be
readily explained by the higher hydrogen peroxide formation
rates observed for these compounds. Formaldehyde also
Table 2. Preliminary substrate scope of the photochemobiocatalytic
[
a]
hydroxylation reaction.
suppressed H
concentration of H
formation was somewhat diminished in the enzymatic reaction
rate might be explained by two effects. On the one hand, the
2 2
response of the enzyme to a higher H O formation rate is non-
linear, as at some point the enzyme approaches its maximum
turnover rate. On the other hand, the experiments with methanol
are automatically superimposed by the reaction rate of
formaldehyde and formate as they are formed during the
reaction. This would be more pronounced in the photoenzymatic
2
O
2
degradation, resulting in a higher steady state
. The fact that the increase in peroxide
Entry
product
mM ee
[%]
Other products mM GC-
TON
2
O
2
yield (rAaeUPO)
[
b]
-3
[%]
10
1
6
.6
-
-
0.5 92.4
0.3 >99
43.9
61.5
2
3
4
9.2
4.3
-
0.4 55.7
28.6
45.8
2 2
experiments than in the photocatalytic H O formation due to the
longer timescale of the experiments which allow for a higher
fraction of the methanol to be converted. Nevertheless,
especially formate may represent an attractive alternative to
methanol as sacrificial electron donor (Figures S24, 25).
Also other alcohols such as ethanol or isopropanol could be
used as sacrificial electron donors to promote the overall
reaction, albeit at lower rates as compared to methanol (Table 1,
entries 13, 14). The relative rates found with ethanol and
isopropanol are in good correlation with the steady-state
concentration and formation rate of H
with the oxidation potentials of the alcohols.
Finally, we also evaluated the substrate scope of the
proposed photochemobiocatalytic reaction sequence (Table 2).
6.9 >99
8.9 95.0
8.0 93.3
1.6
72
5
1.6 91.2
1.3 83.5
59.6
6
7
53.5
17.5
2
O
2
and roughly correlate
1.0 89
Conditions: [substrate] = 10.0 mM, [rutile Au-TiO
1.6 67.8
[
10]
[
a]
-1
2
] = 10 gL , [rAaeUPO] =
150 nM, [MeOH] = 250 mM in phosphate buffer (pH 7.0, 60 mM), T = 30 °C,
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COMMUNICATION
[
b]
-
[15]
7
;
0 h, under illumination; = [alcohol]final  ([ketone]final + [starting material]final)
redox potentials of water to hydroxyl radicals, +2.8 V,
and
1
[16]
methanol to methanol radicals, +1.2 V, respectively. Moreover,
due to the strongly reducing nature of the methanol radical (-
The regio- and enantioselectivity was essentially the same
as in previous studies. The only side reaction observed was a
minor overoxidation to the corresponding ketone as described
above.
Very pleasingly, high turnover numbers could be achieved
throughout these experiments that compare well with the
1.3 V), it can readily inject an electron into TiO , forming
2
formaldehyde and resulting in up to two conduction band
electrons per reactive photon, an effect also known as current
[
17]
doubling (Figure S32).
Hence, methanol oxidation not only
accelerated the H O2 generation rate but also prevented the
2
numbers reported so far with more complicated in situ H
2
O
2
formation of ROS from water oxidation (Figure S32 and Table
S3 for further details).
[1b]
[18]
generation systems.
Hence, we are optimistic that further
optimisation of the reaction setup may well lead to an
economically attractive oxyfunctionalisation reaction. Indeed, a
preparative scale hydroxylation reaction of ethyl benzene
yielded more than 100 mg of essentially enantiopure product
Overall, this study demonstrates the application of methanol
as sacrificial reductant for in situ H O2 generation from O2 to
2
promote selective, peroxygenase-catalysed oxyfunctionalisation
reactions. Admittedly, the productivities reported here do not
reach preparatively useful values yet. Also the very high
turnover numbers for rAaeUPO reported previously have not
been reached yet. Future efforts will therefore focus on
optimizing the light penetration into the reaction medium and
(
75% conversion, 51% isolated yield). Further optimisation is
currently underway.
increasing the
photochemical flow-chemistry setups
internal illumination.
H
2
O
2
generation rate, e.g. by using
[
19]
or wirelessly powered
[
20]
Acknowledgements
F.H and W.Z. gratefully acknowledge financial support by the
European Research Council (ERC Consolidator Grant No.
648026). B.O.B. and J.Z.B are grateful for financial support from
Figure 2. Qualitative and quantitative determination of radicals occurring
the German Research Foundation (DFG, grant no. BL 1425/1-1).
The authors thank Ben Norder (Delft University of Technology)
for XRD, Dr. Wiel H. Evers (Delft University of Technology) for
TEM and Prof. Fred Hagen (Delft University of Technology) for
EPR measurements.
during the photocatalytic process. (A) EPR spectra recorded during the
illumination of and rutile Au-TiO
2
in water with methanol for 20 min. Signals
marked with asterisk () belong to the existing oxidation product of DMPO,
[
12]
5
,5-dimethyl-2-oxopyrroline-1-oxyl (DMPOX). Signals marked with triangles
() belong to the spin-adduct •DMPO-OH. Signals marked with circles ()
[
13]
belong to the spin-adduct •DMPO-CH
2
OH from methanol.
Reaction
-
1
condition: [Au-TiO
2
] = 5 g L , [DMPO] = 30 mM, [methanol]= 100 mM, RT,
Keywords: Biocatalysis • Photocatalysis • Oxyfunctionalisation •
under illumination; (B) Time course of the photocatalytic umbelliferone
TiO • Peroxygenase
2
generation from coumarin as a specific detection method for •OH radicals.
-
1
Reaction conditions: 60 mM phosphate buffer (pH 7), [Au-TiO
2
] = 5 g L ,
o
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2
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[
[
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absence of methanol (Figure 2B). Upon addition of methanol
[
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10.1002/anie.201708668
COMMUNICATION
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COMMUNICATION
Selective oxyfunctionalisation
reactions are achieved by combining
inorganic photocatalysis with selective
enzymatic oxyfunctionalisation
catalysis.
Wuyuan Zhang, Bastien O. Burek, Elena
Fernández-Fueyo, Miguel Alcalde,
Jonathan Z. Bloh*, and Frank Hollmann*
Page No. – Page No.
Selective activation of C-H bonds by
cascading photochemistry with
biocatalysis
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