Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst for the Borylation of α,β-Unsaturated Acceptors in Aqueous Media

Article abstract of DOI:10.1007/s10562-021-03571-2

Abstract: We have demonstrated that cellulosic CuI nanoparticles could perform as an efficient heterogeneous catalyst for the synthesis of useful organoboron compounds. Desired β-borylation products were all obtained in good to excellent yields under mild

Full text of DOI:10.1007/s10562-021-03571-2

Catalysis Letters
https://doi.org/10.1007/s10562-021-03571-2
Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst
for the Borylation of α,β‑Unsaturated Acceptors in Aqueous Media
Lijie Zhou1,2 · Biao Han1,2 · Yaoyao Zhang1 · Bojie Li1 · Liansheng Wang1 · Jianying Wang2 · Xianbao Wang2 ·
Lei Zhu1,2,3
Received: 4 January 2021 / Accepted: 12 February 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC part of Springer Nature 2021
Abstract
We have demonstrated that cellulosic CuI nanoparticles could perform as an efcient heterogeneous catalyst for the synthesis
of useful organoboron compounds. Desired β-borylation products were all obtained in good to excellent yields under mild
conditions. This catalyst could be recovered easily and still work efectively in six runs. Notably, asymmetric synthesis of
organoboron compounds was accomplished by applying a chiral phosphine ligand. This newly developed protocol provides
an efcient and sustainable pathway for the formation of C-B bonds and largely extends the applied range of cellulose.
Graphical Abstract
Asymmetric and efcient synthesis of organoboron compounds was accomplished by cellulosic CuI nanoparticles combining
with a chiral phosphine ligand. This newly reported strategy provides a green and sustainable method for the construction
of C–B bonds and largely extends the applied range of cellulose.
Keywords Cellulosic CuI nanoparticles · Asymmetric borylation · α,β-Unsaturated acceptors · Aqueous media · Recycle
and reuse
* Yaoyao Zhang
1 Introduction
yaoyaozhang@hbeu.edu.cn
* Xianbao Wang
The development of green and environmentally benign syn-
thetic methodologies has become an important consideration
in current chemical research. In this context, synthesis and
applications of heterogeneous catalysts in organic synthesis
wxb@hubu.edu.cn
* Lei Zhu
Lei.zhu@hbeu.edu.cn
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

L. Zhou et al.
have great developments in the feld of catalysis. In particu-
lar, heterogeneous catalysts which could be recycled and
reused obtained more attention, representing the concept
of green chemistry [1, 2]. Metallic nanoparticles constitute
an important class of heterogeneous catalysts due to their
unique properties and advantages [3–8]. Thus, design and
synthesis of fne nano-catalyst and exploration of its applica-
tions in green synthesis still remain an attractive area.
Organoboron compounds are of great importance both
in pharmacy [9, 10] and synthetic chemistry [11, 12]. Num-
bers of drugs contain functional boron groups, such as tala-
bostat [13], bortezomib [14], delanzomib [15] and so on
[16]. Also, organoboron compounds are versatile building
blocks for chemical synthesis [17]. For example, the result-
ing carbon-boron bonds could be readily transformed into
C–O, C–N and C–C bonds via many kinds of reactions, like
Suzuki–Miyaura cross-coupling [18, 19], 1,2-migration
[20], Petasis reaction [21], allylborations [22] and oxida-
tions [23]. With recent developments, catalytic borylation of
α,β-unsaturated acceptors by using bis(pinacolato)diboron
(B2(pin)2, 1) was proved to be an efcient and direct pathway
to achieve organoboron compounds [24–27]. Based on this
strategy, a series of methods with diferent metals including
palladium [28], platinum [29], nickel [30], rhodium [31],
zinc [32] and copper [33–41] were reported. Besides, N-het-
erocyclic carbenes were also efective catalysts [42]. Among
all of them, copper was more attractive because it is green,
cheap and abundant. In spite of impressive progress, most of
them sufered from certain limitations, such as high catalyst
loading (5–10 mol%), use of harsh conditions (strong base),
expensive ligands, which restrict the large-scale applica-
tion in industry. Therefore, development of highly reactive
copper nanoparticles for the borylation of α,β-unsaturated
acceptors in mild conditions is still in high demand.
performance as highly reactive and recyclable catalysts for
the boron conjugate additions of α,β-unsaturated acceptors
in aqueous media without any additive. Remarkably, boryla-
tion in asymmetric manner was also achieved by using a
chiral phosphine ligand.
2 Materials
Cellulose (50 μm, CAS: 73183-34-3) was purchased from
J&K (Beijing, China), bis(pinacolato)-diboron (CAS:
73183-34-3) was purchased from Energy Chemical (Shang-
hai, China) and copper salts were purchased from Nine-Dinn
Chemistry (Shanghai, China). All α,β-unsaturated acceptors
were obtained commercially from Energy Chemical (Shang-
hai, China) or synthesized following known literature. Cel-
lulosic CuI nanoparticles (Cell@CuI NPs) were prepared
in the following method, as literature reported [49]. Sus-
pension of CuI (0.19 g, 1.0 mmol) and cellulose (2.0 g) in
methanol was stirred at room temperature overnight. The
resulted mixture was fltered and the residue was washed by
methanol and acetone. The obtained white solid was dried at
50 °C for 12 h under vacuum. The obtained Cell@CuI NPs
were then characterized by IR, XRD, EDS, SEM, TEM and
ICP. The copper loading of Cell@CuI NPs was found to be
0.36 mmol/g, determined by ICP-OES.
3 Results and Discussion
3.1 Characterization of Cell@CuI
The coordination of CuI on cellulose and the stability of
Cell@CuI NPs were verified by FT-IR (Fig. 1). When
CuI was supported on cellulose, the intensity of broad
band belongs to the hydroxyl group in cellulose decreased
appreciably. Upon coordination, the characteristic band at
around 439 cm−1 increased in the spectra of Cell@CuI NPs
(Fig. 1b), which was due to the coordination of the copper
ions to hydroxyl (-OH) groups of the cellulose [50].
To the best of our knowledge, only a few examples
related to copper nanoparticles catalyzed borylation of α,β-
unsaturated acceptors were reported. Xu and Huang [43]
found that copper nanoparticles on carbon black were able to
catalyze the borylation of α,β-unsaturated ketones by using
toluene as the solvent and methanol as the additive. In our
previous work [44–46], we immobilized copper nanoparti-
cles on a chitosan/poly(vinyl alcohol) composite flm and
found that it was very active in organic synthesis. However,
both examples were based on Cu(0) catalyst and no asym-
metric synthesis was disclosed. On the other hand, cellulose,
an abundant biopolymer, was reported to be applied as the
support of catalyst in Heck reaction [47], aza-Michael reac-
tion [48] and click reaction [49]. With our continued interest
in the development of green synthetic methodologies, we
assumed that cellulose could also be used as the support
for CuI nanoparticles which was capable to catalyze this
borylation process. Hence, we herein report the synthesis
of CuI nanoparticles anchored on cellulose and its novel
ꢀꢀ
a
a
b
b
3348
439
ꢀꢀ
1000
900
800
700
600
500
4000 3800 3600 3400 3200 3000 2800 2600
Wavenumber (cm-1
)
Fig. 1 FT-IR spectra of (a) cellulose, (b) Cell@CuI NPs
1 3

Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst for the Borylation of…
XRD pattern of CuI showed nine peaks at 2θ= 25.2°,
29.1°, 42.0°, 49.5°, 52.0°, 60.9°, 67.0°, 76.9°, 82.5°
(Fig. 2a), while cellulose showed main peak at 2θ= 22.5°
(Fig. 2b). All the difraction peaks and their positions for CuI
matched well with JCPDS card (NO. 01–076-0207) for cubic
CuI. Hence, the XRD spectra of Cell@CuI NPs maintained
the peaks of both CuI and cellulose (Fig. 2c).
cellulose. SEM image of the Cell@CuI NPs indicated
the deposition of nano-sized CuI crystals on cellulose
(Fig. 4c–f). This reveals that CuI was converted to nano
sized CuI and deposited over the surface of cellulose during
the preparation of catalyst, possibly due to very low solubil-
ity of CuI in methanol.
TEM image of cellulose and Cell@CuI NPs (Fig. 5a-d)
further confrmed the presence of CuI on cellulose support
with particle size as average 39 nm. (Fig. 5a vs b). The lat-
tice fringes with d spacings of 2.60 Å corresponding to the
{220} plane can be clearly distinguished, which indicates its
single-crystalline nature [51]. This result is well consistent
with the XRD pattern (Fig. 2).
EDS spectrum (Fig. 3) of the Cell@CuI NPs showed
Cu element, indicated the presence of CuI supported on
c
b
a
3.2 Catalytic Activity of Cell@CuI
After full characterization of this prepared Cell@CuI NPs,
we focused on the exploration of its practical applications
in the synthesis of organoboron compounds. By employing
the β-borylation of chalcone 2a with bis(pinacolato)diboron
1 as the model reaction, we investigated a range of reaction
conditions. The results were summarized in Table 1. This
reaction showed a very strong solvent efect. Protic solvents
like EtOH, MeOH and H2O gave much better results than
aprotic solvents (entries 1–5). This is because proton source
is essential to accomplish the whole catalytic cycle [35]. To
our delight, H2O gave the best result and it could perform
as both the solvent and proton source. In order to further
improve the conversion, we turned to use aqueous media as
(220)
(111)
(311)
(331)
(422)
(200)
(511)
(400)
60
(222)
20
40
80
Scanning angle, 2θ, Degree
Fig. 2 XRD analysis of (a) CuI, (b) cellulose and (c) Cell@CuI NPs
Fig. 3 EDS spectrum of Cell@
CuI NPs
1 3

L. Zhou et al.
Fig. 4 SEM spectra of cellulose
a 10 μm, b 5 μm, Cell@CuI
NPs before c 10 μm, d 5 μm and
after reaction e 10 μm, f 5 μm
the solvent (entries 6–9), a mixture of H2O and organic sol-
vents. In this case, all substrates were dissolved and it makes
the separation of Cell@CuI NPs become much easier after
the reaction. It was found that the desired product could be
obtained in 82% isolated yield when using the combination
of MeOH and H2O (entry 9).
CuI nanoparticles was the key for the high conversion. In
addition, the reaction didn’t proceed at all in absence of cata-
lyst (entry 16). Thus, we determined the optimized condi-
tions as to run the reaction in MeOH/H2O (v/v=4/1) for 6 h
under air, using Cell@CuI NPs as catalyst (entry 12).
With the optimized conditions in hand, we explored the
substrate scope and the results were summarized in Fig. 6.
Various chalcone derivatives have shown excellent perfor-
mance in aqueous media catalyzed by Cell@CuI NPs with
only 0.9 mol% Cu loading (3a–3k). Both electron-donating
and electron-withdrawing substituents at 4-position of chal-
cones (3b-3e) gave the corresponding products in good to
excellent yields. For chalcones bearing meta-substituted
groups, satisfactory yields were obtained (3f and 3 g). Next,
4′-subtituted chalcones were applied and good to excellent
yields were obtained in all cases (3h–3j). Di-substituted
chalcone was also suitable substrate and desired product 3k
was isolated in 85% yield. When benzyl acrylate was used
as substrate, the β-borylation product 3l could be further
By tuning the ratio of MeOH to H2O (entries 9–11), the
yields of product changed while 4:1 gave a remarkable iso-
lated yield (96%, entry 10). As we have previously reported,
copper nanoparticles exhibited a high reactivity for the for-
mation of C–B bonds [44]. Our prepared Cell@CuI NPs was
also extremely reactive and the reaction could be fnished
in 6 h (entry 12). When the catalyst was reduced to half
amount, the corresponding product could still be obtained
in 82% yield (entry 14). TON and TOF of this catalyst were
calculated to be 105 (entry 12) and 30 h−1 (entry 14), respec-
tively. For comparison, we added cellulose and CuI sepa-
rately as the catalysts. However, the reactivity signifcantly
decreased (entry 15) which indicated that the formation of
1 3

Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst for the Borylation of…
Fig. 5 TEM images of a cel-
lulose, b Cell@CuI NPs before
and c after reaction, d HRTEM
of Cell@CuI NPs
Table 1 Optimization of the reaction conditions
Entry
Catalyst
Solvent
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cell@CuI NPs
Cellulose+CuI
–
THF
acetone
EtOH
MeOH
12
12
12
12
12
12
12
12
12
12
12
6
NR
NR
30
56
70
50
76
55
82
96
70
95
61
82
25
NR
H2O
THF/H2O=1/1
Acetone/H2O=1/1
EtOH/H2O=1/1
MeOH/H2O=1/1
MeOH/H2O=4/1
MeOH/H2O=1/4
MeOH/H2O=4/1
MeOH/H2O=4/1
MeOH/H2O=4/1
MeOH/H2O=4/1
MeOH/H2O=4/1
9
10
11
12
13
14b
15
16
3
6
6
6
a
Reaction conditions: substrate 2a (0.2 mmol), B2(pin)2 1 (1.2 equiv), catalyst 5 mg, solvent (2 mL), room temperature, air; isolated yields of
product; bCell@CuI NPs 2.5 mg was used
NR no reaction
1 3

L. Zhou et al.
Fig. 6 Substrate scope for synthesis of β-boron compounds (Reaction
conditions: substrate 2a (0.2 mmol), B2(pin)2 1 (1.2 equiv),catalyst 5
mg, solvent (2 mL), room temperature, air; isolated yieldsof products)
converted via deprotection treatment. It was found that
α- and β-methyl acrylate both performed well under mild
conditions. It was probably due to the steric hindrance that
the yield of 3m was a little higher than 3n. When α,β-γ,δ-
dienone was used, 1,4-addition product 3o was obtained
exclusively and 1,6-addition byproduct was not detected.
Notably, quaternary carbon could be formed in product 3p
when using a cyclic enone as substrate. Therefore, we have
demonstrated the cellulosic CuI nanoparticles was capable
to catalyze diferent kinds of α,β-unsaturated acceptors.
This newly developed method has shown a good substituent
compatibility under base-free conditions and it is more eco-
friendly to carry out this reaction in aqueous media.
Fig. 7 Substrate scope for synthesis of β-hydroxy compounds (Reac-
tion conditions: substrate 2a (0.2 mmol), B2(pin)2 1 (1.2 equiv), cata-
lyst 5 mg, Solvent (2 mL), room temperature, air; isolated yields of
products)
was obtained exclusively for substrate 4n and 1,6-byprod-
uct was not observed. Substituted benzylideneacetones
were also suitable substrates (4o–4q). This transformation
provided a powerful strategy for late-stage modifcation of
natural products which have α,β-unsaturated carbonyls.
Next, we selected 2d as substrate and largely increased
the reaction scale. The corresponding product 3d could also
be achieved in 90% yield on a preparative scale (Scheme 1a).
As previously mentioned, boron substituent installed by our
strategy is a versatile building block in organic synthesis.
As illustrated, product 3c was smoothly transformed into
trifuoroborate salt 5c in the presence of KHF2 (aq.) with
MeCN in a good yield (Scheme 1b). Product 5c could be
further applied in the well-known Suzuki–Miyaura coupling.
In order to demonstrate the practical utility of our devel-
oped protocol, we applied a one-pot strategy which con-
verted α,β-unsaturated acceptors to β-hydroxy products 4
straightly (Fig. 7). The crude mixture after borylation can
undergo oxidation directly without any additional treatment.
We carried out the oxidation of 3 by using a simple method
with excess amount of sodium peroxyborate. The conversion
to β-hydroxy product 4 was completed in almost quantitative
yield. Chalcone derivatives bearing both electron-donating
and electron-withdrawing groups all proceeded smoothly to
give the desired β-hydroxy products in moderated to good
yields (4a–4k). Remarkably, thiophene group was tolerated
under this reaction condition (4l, 4m). 1,4-Addition product
3.3 Recyclability Study of Cell@CuI
The reusability and stability are highly important for het-
erogeneous catalyst both from economic and environmental
point of view. When the reaction was completed, Cell@CuI
NPs could be easily recycled by simple fltration. After being
1 3

Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst for the Borylation of…
a
Gram scale synthesis
O
O
B(pin)
Cell-CuI NPs
O
O
O
(0.9 mol% Cu)
B
B
+
MeOH/H2O = 4/1
r.t., 6 h, air
O
Br
Br
3d
2d
1
, 3.0 mmol
90%, 1.12 g
b
Transformation of product
O
B(pin)
O
BF3K
aq. KHF2
MeCN/H2O
r.t., overnight
Cl
Cl
5c
, 92%
Scheme 1 a Gram scale synthesis of 3d, b transformation of product 3c
washed and dried, we sent the catalyst for the next run of
reaction in same scale. Remarkably, desired product was all
obtained in excellent yields for six consecutive cycles and no
signifcant decrease was observed (Fig. 8). In all cycles, the
recovery ratios of catalyst were all above 90% (details see
SI Table S1). SEM and TEM images of recovered Cell@CuI
NPs showed similar results as before, which indicated the
stability of this catalyst (details see SI Page S5). This result
suggested that cellulose could also be used as an efective
support for this borylation process, as well as chitosan [44]
and carbon black [43]. The newly developed protocol based
on Cell@CuI NPs even owned a higher reactivity and much
easier way for catalyst preparation. To check the stability of
catalyst, we examined the metal leaching of fltrate which
come from the fltration of reaction mixture. After remov-
ing the catalyst, almost no detectable copper leaching was
found in the residue by ICP-OES analysis. This observation
was consistent with the high recovery ratios and reactivities
of catalyst which we have disclosed for each recycled run.
3.4 Asymmetric Borylation Catalyzed by Cell@CuI
Asymmetric synthesis of organoboron compounds was
extremely important for the research of this area. Yun [52]
reported Cu(I) catalyzed enantioselective β-borylation of
α,β-unsaturated acceptors by using chiral josiphos ligand,
while Kobayashi [37–41] applied Cu(II) with a chiral
2,2′-bipyridine ligand. Then we checked the possibility to
Fig. 8 Recycle and reuse of
Cell@CuI NPs
1 3

L. Zhou et al.
run this reaction in asymmetric manner by combining Cell@
CuI NPs with diferent chiral ligands (Fig. 9). Surprisingly,
(R)-(S)-josiphos gave satisfactory results after 12 h reac-
tion and product 6a was achieved in 72% yield with excel-
lent enantioselectivity (97% ee). In previous Cu(I) catalytic
system, strong base (e.g. NaOtBu) was required and alco-
hol additive was used for rate acceleration. In addition, the
reaction was usually carried out in organic solvents with
anhydrous conditions because H2O may diminish the enan-
tioselectivity in this case. However, our method could work
without any use of strong base, running in aqueous phase
at room temperature. This result provided a new protocol
to activate Cu(I) species in enantioselective β-borylation of
α,β-unsaturated acceptors.
using CD3OD/D2O as the solvent (details see SI Page S6).
The Cell@CuI NPs react with B2(pin)2 to form copper boryl
complex B. The conjugate addition of B to α,β-unsaturated
acceptors occurred via intermediate C to generate organo-
copper species D, which was then protonated with MeOH
or H2O to yield the product. MeOH and H2O could perform
as both the solvent and proton source during this catalytic
cycle. In asymmetric manner, chiral phosphine CuI com-
plex controlled the boron conjugate addition step via a
CuI-C-enolate intermediate, leading to the enantioselective
formation of products (Fig. 11) [53].
4 Conclusions
Encouraged by this result, we started to explore the sub-
strate scope for the asymmetric synthesis of organoboron
compounds. Gratifyingly, chalcone derivatives were almost
converted efciently to give the desired products in moderate
yields with excellent enantioselectivities (6b–6g) (Fig. 10).
Further improvements in reactivity by modifying the struc-
ture of cellulose are now ongoing in our lab.
In conclusion, we have reported the frst example of cel-
lulosic CuI nanoparticles catalyzed boron conjugate addi-
tions of α,β-unsaturated acceptors in aqueous media. After
preparation and characterization of the catalyst, a mild
and eco-friendly methodology was successfully developed
by applying this CuI NP catalyst towards the synthesis of
organoboron compounds. This new protocol has shown a
good generality and functional group tolerance. Various
α,β-unsaturated acceptors could be converted to the cor-
responding products in good to excellent yields. Based on
the high activity of our catalyst, gram scale synthesis was
3.5 Proposed Mechanism
In order to disclose the mechanism of this unusual Cell@
CuI NPs catalyzed borylation, we tested the reaction by
Fig. 9 Enantioselective
β-borylation of chalcone with
diferent chiral ligands
1 3

Cellulosic CuI Nanoparticles as a Heterogeneous, Recyclable Catalyst for the Borylation of…
O
OH
O
OH
O
OH
Me
6b, 64% yield, 97% ee
OH
Cl
6c, 76% yield, 91% ee
OH
OMe
6d, 48% yield, 95% ee
OH
O
O
O
Me
Me
F
Br
6e, 52% yield, 95% ee
6f, 75% yield, 97% ee
OH
6g, 50% yield, 93% ee
OH Cl
O
O
MeO
MeO
6h, 47% yield, 95% ee
6i, 43% yield, 96% ee
Fig. 10 Asymmetric synthesis of organoboron compounds (Reaction conditions: substrate 2 (0.2 mmol), B2(pin)2 1 (1.2 equiv), catalyst 5 mg,
chiral ligand L1 (0.024 mmol), solvent (2 mL), room temperature, 12 h, air); aIsolated yields of products
conditions, reuse of catalyst, good functional group compat-
ibility as well as excellent enantioselectivities.
Supplementary Information The online version of this article (https://
doi.org/10.1007/s10562-021-03571-2) contains supplementary mate-
rial, which is available to authorized users.
Acknowledgements The authors acknowledge the financial sup-
port from the National Natural Science Foundation of China (No.
21774029), the Natural Science Foundation of Hubei Province of China
(Nos. 2019CFB237, 2019CFB354), Hubei University Excellent Young
and Middle-aged Science and Technology Innovation Team Project
(No.T201816), the Natural Science Foundation of Xiaogan City (Nos.
XGKJ201910047, XGKJ2020010053). Lei Zhu thanks the “Chutian
Scholar” Program of Hubei Province. Lijie Zhou and Biao Han thanks
the High Level Master Degree Thesis Cultivation Project of Hubei
Engineering University.
Declaration
Conflict of interest The authors declare that they have no confict of
Fig. 11 A proposed mechanism
interest.
achieved. Besides, the CuI nanoparticles could be easily
recovered and reused for six cycles and no signifcant loss
of activity was observed. Remarkably, asymmetric synthesis
was successfully developed in aqueous phase without any
base towards this Cu(I)-based catalyst. The advantages of
this newly described strategy include easy handling, mild
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Authors and Afliations
Lijie Zhou1,2 · Biao Han1,2 · Yaoyao Zhang1 · Bojie Li1 · Liansheng Wang1 · Jianying Wang2 · Xianbao Wang2 ·
Lei Zhu1,2,3
1
3
School of Chemistry and Materials Science, Hubei
Engineering University, Xiaogan 432000, China
Hubei Key Laboratory of Bioinorganic Chemistry & Materia
Medica, Huazhong University of Science and Technology,
Wuhan 430074, China
2
School of Materials Science and Engineering, Hubei
University, Wuhan 430062, China
1 3