Halofunctionalization of alkenes by vanadium chloroperoxidase from: Curvularia inaequalis

Article abstract of DOI:10.1039/c7cc03368k

The vanadium-dependent chloroperoxidase from Curvularia inaequalis is a stable and efficient biocatalyst for the hydroxyhalogenation of a broad range of alkenes into halohydrins. Up to 1 200 000 TON with 69 s^-1 TOF were observed for the biocatalyst. A bienzymatic cascade to yield epoxides as reaction products is presented.

Full text of DOI:10.1039/c7cc03368k

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Halofunctionalization of alkenes by vanadium chloroperoxidase
from Curvularia inaequalis
Jia Jia Dong, †a Elena Fernández-Fueyo, †a Jingbo Li,b Zheng Guo,b Rokus Renirie,c Ron Wever,c and
Frank Hollmanna*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The vanadium-dependent chloroperoxidase from Curvularia 1.11.1.8, 1.11.1.10 and 1.11.1.18). These enzymes generate
inaequalis is stable and efficient biocatalyst for the reactive hypohalites from the corresponding halides and
a
hydroxyhalogenation of a broad range of alkenes into halohydrins. hydrogen peroxide. This has been reported for example using
Up to 1.200.000 TON with 69 s-1 TOF were observed for the the heme-dependent chloroperoxidase from Caldariomyces
biocatalyst. A bienzymatic cascade to yield epoxides as reaction fumago (CfuCPO).8 However, the poor stability of heme-
products is presented.
dependent haloperoxidases against H2O2 limits the broad
applicability of this enzyme class and make control over the in
situ concentration of H2O2 inevitable.9 In fact, the catalytic
performance (in terms of turnover numbers, TON) reported for
CfuCPO is too low to be of preparative value (generally a few
thousand turnovers can be estimated from the
publications).8c,10 Vanadium-dependent haloperoxidases are
principally more robust against H2O2 and therefore maybe
more practical catalysts.11
Vic-halohydrins are valuable building blocks e.g. in natural
product synthesis.1 Two functional groups endow the organic
chemist with handles for further transformations such as
conversion into epoxides and other fuctionalities.2 To attain
vic-halohydrins, halohydroxylation of olefins appears to be the
most direct approach next to ring-opening of epoxides by
nucleophilic attack.3
Treatment of olefins with elementary halogens in water
provides halohydrins. This approach, however, is hampered by
the high reactivity of the reagents leading to side products and
the corrosive reaction conditions.4 Also the formation of
significant inorganic wastes renders this approach
questionable from an environmental point of view. Therefore,
N-halo compounds such as N-halosuccinimide represent the
most commonly used reagents, or sodium periodate, despite
the fact of low atom efficiency causing large amounts of waste
products.5 More recently, transition metal catalysts (including
W and V) have received increasing interest for the conversion
of alkenes to halohydrins using H2O2 and inorganic halide as
reagents.6 In addition, oxone has been successfully applied as
oxidant using NH4Cl as halogen source.7
The vanadium chloroperoxidase from Curvularia inaequalis
(CiVCPO) for example excels by its superb stability against H2O2
as well as demanding environmental conditions such as
cosolvents and temperature.12 It was successfully applied for
the catalytic halogenation of phenols13 as well as to mediate
the (Aza-) Achmatowicz reaction.14
Finally, biocatalysis also in principle enables the conversion of
alkenes to halohydrins using so-called haloperoxidases (E.C.
Scheme 1. Chemoenzymatic oxidation of alkenes using the vanadium chloroperoxidase
from Curvularia inaequalis (CiVCPO) as hypohalite generation catalyst. Here, the most
popular chemo-enzymatic mechanism is shown wherein the enzyme forms the
hypohalite in situ followed by spontaneous reaction of the latter with an alkene. It
should, however be mentioned that also some indications for a direct enzymatic
halohydroxylation within the enzyme active site exist.11
Therefore, we became interested in evaluating CiVCPO as
catalyst for the halogenation of alkenes striving for more
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robust reactions than reported for the heme-dependent (Britton-Robinson) buffer (Table 1, entries 4 and 5). Raising or
halogenases (Scheme 1). lowering the pH value lead to dramatic activity decreases.
In first set of experiments we investigated the Under acidic reaction conditions the bromohydrin was the
a
halohydroxylation of styrene. As starting point we chose the predominant / sole product of the reaction. The relative
optimised reaction conditions determined previously.13, 14 Full epoxide yield increased with increasing pH. This is consistent
conversion was achieved after 4 hours with high selectivity with the well-known base-catalysed ring-closure of
towards vic-bromohydrin (>90%) with only trace amount of halohydrins.
side products (epoxide, ketone derivatives) detectable (Table To obtain further insights into the kinetics of the
1, entry 2). The regio chemistry of the hydroxybromination hydroxybromination reaction, we followed the time course of
reaction exclusively followed Markovnikov’s rule. In the chemoenzymatic conversion of (water soluble) sodium
accordance with the suspected chemo-enzymatic reaction styrene-4-sulfonate 1g (Figure ). Following a very short lag-
mechanism, no enantioselectivity was observed. When the phase, the product accumulation proceeded linearly until
enzyme was omitted from the reaction, no product formation approx. 75% conversion and then considerably slowed down.
was observed (Table 1, entry 3), which confirms the proposed After 5-6 h, full conversion was obtained. It is worth
chemoenzymatic cascade. Likewise, no conversion was emphasising the excellent catalytic performance of the
observed in the absence of H2O2 or KBr (data not shown).
biocatalyst here: Over 6.5 h CiVCPO performed 400.000
catalytic turnovers corresponding to an average turnover
frequency of more than 15 s-1 (over 6.5h). Within the first 2 h,
this value was even higher (69 s-1). Raising the concentration of
1g from 40 mM to 160 mM (while concomitantly increasing
the concentration of KBr as well as the buffer strength to avoid
Table 1. Characterisation of the reaction conditions for the chemoenzymatic
bromohydroxylation of styrene.
pH shifts, vide infra) resulted in 80 % of the desired product 2g
.
Hence CiVCPO performed at least 1.280.000 catalytic cycles.
These values underline the robustness and efficiency of the
biocatalyst.
Yield Yield
KBr
b)
H2O2
b)
Conversion
Entry
pHa)
Solvent
2a %
3a %
d)
c)
%
d)
1
2
3 e)
4 f)
5 f)
6
3
H2O
H2O
160
160
160
160
160
160
20
170
170
170
170
170
170
170
170
10
full
0
8
n.d.
2
5
90
0
5
H2O
0
water
H2O
full
full
13
45
50
41
40
4
55
52
8
7
9
5
5
H2O
H2O
7
H2O
40
25
0
8
H2O
160
7
/EtOH
(2 : 1)
H2O
9 g)
5
160
110
full
90
2
a) buffers used: acetate (pH 3), citrate (pH 5) and Britton-Robinson (pH 7 and 9);
b) Concentration units (mM); c) determined by 1H NMR; d) NMR yield determined
from the crude reaction mixture; e) Control reaction in the absence of CiVCPO; f)
20 hours reaction time; g) portion-wise addition of H2O2.
When using ethanol a cosolvent, also very significant amounts
(13 %) of (2-bromo-1-ethoxyethyl)benzene were obtained
(Table 1, entry 8). We attribute this to the competition of
water and ethanol as nucleophiles.
Figure 1. Time course of the chemoenzymatic oxidation of alkene 1g (ꢀ) to 2g (ꢀ).
General conditions: aqueous medium (D2O, 0.1 M citrate pH 5), c(1g) = 40 mM, c(KBr) =
160 mM, c(H2O2) = 170 mM, c(CiVCPO) = 100 nM, T = 25oC. The concentration of
substrate and product was determined by 1H NMR (see ESI).
Adding the oxidant (H2O2) portion-wise proved to be more
efficient than a single addition at the beginning of the reaction
(Table 1, entries 2 vs. 9). This can be attributed to a the well-
known formation of singlet oxygen (1O2) from hypohalites and
H2O2, which in our case represents an undesired side reaction
consuming H2O2.15
Applying the optimised reaction conditions (Table 1, entry 9)
we advanced to evaluate the product scope of the chemo
enzymatic hydroxyhalogenation reaction. As shown in Figure 2
both aromatic and aliphatic alkenes were converted into the
corresponding halohydrins. Styrene was transformed into the
corresponding bromohydrin 2a and chlorohydrin 2b with 81%
and 77% yield, respectively. α- and β-Methylstyrene were
converted in satisfactory yields. The (E)/(Z) configuration of
Varying the pH value of the reaction medium had the most
significant effect on the reaction (Figure S1). Consistent with
previous observations, highest CiVCPO activity was observed at
slightly acidic to neutral conditions. Even in the absence of
buffer, essentially the same results were observed as using BR
2 | J. Name., 2012, 00, 1-3
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the latter influenced the product conformation leading to the pH followed by a base treatment to pH 10 with NaOH. This
anti-bromohydrin 2d in case of the (E)-starting material and method proved to be successful for most products with the
syn-bromohydrin 2e from the (Z)-substrate. Allylbenzene 1f exception of the halohydrin obtained from oleic acid (2k).
shows lower reactivity, yielding 51% bromohydrin 2f at 63 % Here, intensive foaming (of the carboxylate) interfered with
conversion. Exchanging bromide by chloride generally lead to a product isolation, which could be avoided by substituting
slight reduction in yields with the exception of 4- NaOH with trimethylamine. Also, it is worth mentioning here
styrenesulfonic acid 1h where next to the desired chlorohydrin that
2h also approx. 10% of 4-formylbenzenesulfonate were ethoxyoctadecanoic acid was also retained here (approx. 30%
observed (Figure 2). yield).
the
previously
mentioned
10(9)-bromo-9(10)-
Likewise, aliphatic alkenes were also converted smoothly: 2- Even though this two-step procedure was efficient for the
bromocyclohexan-1-ol 2i and 1-bromoheptan-2-ol 2j were production of epoxides, we envision a more elegant (and less
obtained in good yields (88% and 80%, respectively). Due to its wasteful) approach. For this, we evaluated a bienzymatic
hydrophobicity, oleic acid required some cosolvent to enhance cascade reaction comprising CiVCPO-initiated halohydrin
its solubility enabling an 62% yield of the bromohydrin 2k. The formation followed by halohydrin dehalogenase (HHe)-
lower
yield
is
due
to
the
10(9)-bromo-9(10)- catalysed ring-closure (Scheme 2). Such a cascade would, in
ethoxyoctadecanoic acid formation as side product as ethanol principle, also allow for catalytic use of the halides. For this, we
competed as nucleophile (Figure 2).
recombinantly expressed the HHe from Agrobacterium
radiobacter. Particularly, its poor enantioselectivity appeared
attractive in this case as a more enantioselective version would
lead to kinetic resolution of the racemic bromohydrin and
consequently in decreased yields of the desired epoxide.16
Scheme 2. Envisioned cascade for the direct transformation of alkenes (e.g. styrene)
into epoxides by combining the CiVCPO-initiated halohydrin formation to ring-closure
catalysed by a halohydrin dehalogenase (e.g. from Agrobacterium radiobacter, ArHHe).
A reaction employing 20 mM styrene 1a in the presence of 5
mM KBr indeed gave 6.6 mM of the desired epoxide and 1.8
mM of the bromohydrin indicating the principal feasibility of
the reaction shown in Scheme 2, despite the reduced activity
of biocatalysts at pH 7 (Figure S2).
The present study underlines the synthetic potential of the
vanadium-dependent chloroperoxidase from Curvularia
inaequalis. Its high robustness and activity enabled efficient
halohydroxylation of various alkenes to the corresponding
halohydrins on preparative scale. Despite the promising first
results, a range of issues will have to be overcome to render
this method truly practical. First, efficient in situ H2O2
generation systems17 will be applied to this reaction in order to
circumvent the undesired 1O2 formation reaction. Also the
envisioned bienzymatic cascade forming epoxides from
alkenes (while using catalytic amounts of halides) will need
further improvements such as the application of CiVCPO
mutants with engineered pH optima,18 reaction engineering
Figure2. Preliminary substrate scope of the chemoenzymatic hydroxyl halogenation
scheme. Reaction condition: c(CiVCPO)= 100 nM, c(alkene) = 40 mM, c(KX) = 160 mM,
c(H2O2)= 170 mM, citrate buffer (0.1 M, pH 5), T= 25 oC, t = 20 h. a) Isolated yield; b) 1
H
NMR yield. c) Ethanol as co-solvent; d) yield of two regioisomers (see ESI).
Preparative scale (1.1 gram) reactions of some selected
alkenes were performed. For example styrene 1a was
converted almost quantitatively albeit at lower selectivity than
shown in Figure 2. After 24h the desired bromohydrin was
isolated in only 50% yield whereas styrene oxide accumulated
to overall 30%. We attribute this to the prolonged reaction
time and an alkaline shift of the reaction pH value favouring
the ring-closure reaction. Future experiments with pH control
are likely to circumvent this current limitation.
approaches
compartments and immobilized enzymes.19
This study was funded by The Netherlands Organisation for
utilizing
spatially
separated
reaction
Nevertheless, we became interested in the further
transformation of the halohydrins into epoxides. The pH
optimum of CiVCPO within the acidic range does not allow for
efficient concurrent hydroxyhalogenation and ring closure.
This may be circumvented by a two-step procedure wherein
the halohydrin formation reaction is performed first at acidic
Scientific Research (NWO) through
724.014.003).
a VICI grant (no.
Notes and references
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