Recyclable Copper Nanoparticles-Catalyzed Hydroboration of Alkenes and β-Borylation of α,β-Unsaturated Carbonyl Compounds with Bis(Pinacolato)Diboron

Article abstract of DOI:10.1002/adsc.202001616

Nano-ferrite-supported Cu nanoparticles (Fe-dopamine-Cu NPs) catalyzed anti-Markovnikov-selective hydroboration of alkenes with B₂pin₂ is reported under mild reaction conditions. This protocol can be applied to a broad range of substrates with high functional group compatibility. In addition, we demonstrated the use of Fe-dopamine-Cu NPs as a catalyst for the β-borylation of α,β-unsaturated ketones and ester, providing alkylboronate esters in up to 98% yield. Reuse of the magnetically recyclable catalyst resulted in no significant loss of activity in up to five reaction runs for both systems. (Figure presented.).

Full text of DOI:10.1002/adsc.202001616

FULL PAPER
DOI: 10.1002/adsc.202001616
Very Important Publication
Recyclable Copper Nanoparticles-Catalyzed Hydroboration of
Alkenes and β-Borylation of α,β-Unsaturated Carbonyl
Compounds with Bis(Pinacolato)Diboron
Mahadev L. Shegavi,a Suresh Saini,a Ramesh Bhawar,a
Meghana Desai Vishwantha,a and Shubhankar Kumar Bosea,*
a
Centre for Nano and Material Sciences (CNMS), JAIN (Deemed-to-be University), Jain Global Campus, Bangalore-562112,
India
E-mail: b.shubhankar@jainuniversity.ac.in
Manuscript received: December 31, 2020; Revised manuscript received: February 23, 2021;
Version of record online: March 9, 2021
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202001616
Abstract: Nano-ferrite-supported Cu nanoparticles (Fe-dopamine-Cu NPs) catalyzed anti-Markovnikov-
selective hydroboration of alkenes with B2pin2 is reported under mild reaction conditions. This protocol can be
applied to a broad range of substrates with high functional group compatibility. In addition, we demonstrated
the use of Fe-dopamine-Cu NPs as a catalyst for the β-borylation of α,β-unsaturated ketones and ester,
providing alkylboronate esters in up to 98% yield. Reuse of the magnetically recyclable catalyst resulted in no
significant loss of activity in up to five reaction runs for both systems.
Keywords: Alkenes; Alkylboronate esters; β-Borylation; Copper; Heterogeneous Catalysis; Hydroboration
Introduction
systems such as Rh and Ir.[10] However, high cost,
inherent toxicity and limited abundance are drawbacks
Alkylboronate esters find important applications in associated with the use of such metals has driven the
pharmaceutical industry, materials and synthetic organ- development of non-precious 3d-transition metal-based
ic chemistry.[1–3] These derivatives are the key nucleo- catalyst systems[11] (Cu,[12] Co,[13] Fe,[14] and Mn[15]).
philic component of CÀ C, CÀ O, and CÀ N cross-
Despite several excellent catalysts having been
coupling reactions due to their bench stability, ease of developed based on homogeneous Earth-abundant
handling, high functional group compatibility and low metals for the hydroboration of alkenes, these catalyst
toxicity.[4] The traditional synthesis of alkylboronic systems suffer from the inability to recover the
acid derivatives was based on the reaction of highly catalyst, which limit their applications in industrial
reactive alkyl lithium or alkyl magnesium reagents manufacturing. Therefore, the use of recyclable metal
with trialkyl borates, followed by hydrolysis or trans- nanoparticles (NPs) based catalysts with low cost and
esterification. However, synthetic applicability of this high efficiency are in great demand from a standpoint
approach is limited due to the poor functional-group of environmental and sustainable chemistry.[13] How-
compatibility.[5] To overcome this challenge recent ever, to date, only a handful of examples of heteroge-
strategies for preparing alkyl boronates include hydro- neous catalytic systems for the hydroboration of
boration of alkenes,[6] metal-catalyzed direct CÀ H unsaturated hydrocarbons have been reported.[16] More-
borylation of alkanes,[7] Miyaura-type borylation of over, these systems have limited functional group
alkyl halides[8] and β-borylation of α,β-unsaturated compatibility[17] and the substrate scope is typically
carbonyl compounds.[9] Catalytic regio- and stereo- restricted to alkynes[18] and electron-deficient alkenes.
selective hydroboration of alkenes with borane deriva- Therefore, the development of an efficient heteroge-
tives and diboron reagents is an attractive approach for neous catalytic system is particularly attractive for the
the synthesis of valuable alkylboronate esters. Signifi- hydroboration of alkenes. Furthermore, using bis
cant examples comprise precious metal-based catalyst (pinacolato)diboron (B2pin2) instead of borane deriva-
Adv. Synth. Catal. 2021, 363, 2408–2416
2408
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
tives as a boron source is more convenient due to its
stability towards air and moisture.
Table 1. Conditions for the nanoparticles catalyzed hydrobora-
tion of styrene (1a).[a]
We previously reported[19] an efficient nano-ferrite-
supported Cu catalyst for the borylation of alkyl
halides, including benzyl chlorides and bromides with
alkoxy diboron reagents under mild reaction
conditions.[19a] Copper is an attractive alternative to the
commonly used noble metals due to its low toxicity,
low environmental impact, high abundance, and low-
cost. Herein we describe magnetically separable Cu-
nanoparticles
(Fe-DOPA-Cu
NPs;
DOPA=
dopamine)[19a,20] catalyzed regioselective hydroboration
of alkenes with B2pin2 under mild reaction conditions.
In addition, Fe-DOPA-Cu NPs catalyzes the β-
borylation of α,β-unsaturated ketones and esters to
furnish alkylboronate esters, with good functional-
group compatibility.
[b]
°
Entry Catalyst (NPs) Base
Solvent T ( C) Yield (%)
1
2
3
4
5
6
7
8
Fe-DOPA-Cu KOtBu Toluene 80
Fe-DOPA-Cu KOtBu Benzene 80
92
90
94
Fe-DOPA-Cu KOtBu MTBE 80
Fe-DOPA-Cu KOtBu DMF
Fe-DOPA-Cu KOtBu DMF
80
99
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
99 (89)[c]
06
Fe3O4
KOtBu DMF
Fe3O4-DOPA KOtBu DMF
11
trace
81
68
68
Results and Discussion
–
KOtBu DMF
The nano-ferrite-supported Cu catalyst (Fe-DOPA-Cu
NPs) was synthesized and analyzed with transmission
electron microscopy (TEM) and X-ray photoelectron
spectroscopy (XPS) to determine their particle size and
oxidation states, respectively.[19a] XPS analysis con-
firmed the presence of Cu in +2 oxidation state on the
solid surface. The inductively coupled plasma mass
spectrometer (ICP-MS) analysis showed that the Cu
loading is 3.45 wt%.
9
Fe-DOPA-Cu LiOtBu DMF
Fe-DOPA-Cu NaOtBu DMF
Fe-DOPA-Cu KOMe DMF
Fe-DOPA-Cu NaOMe DMF
10
11
12
13
41
Fe-DOPA-Cu -
DMF
trace
96
14[d] Fe-DOPA-Cu KOtBu DMF
[a] Reaction conditions: 1a (0.25 mmol, 1 equiv.), Fe-DOPA-
Cu NPs (25 mg), base (1.5 equiv.), B2pin2 (1.5 equiv.),
solvent (1 mL), MeOH (5 equiv.) for 24 h unless otherwise
stated.
[b] Yields were determined by 1H NMR spectroscopy using
nitromethane as an internal standard.
Fe-DOPA-Cu NPs-Catalyzed Hydroboration of Al-
kenes
[c] Isolated yield after chromatographic workup.
[d] Reaction performed in air.
We began our investigation to evaluate the catalytic
performance of the NPs towards the hydroboration of
styrene (1a) as the model substrate (Table 1). The anti-
Markovnikov-selective hydroboration product 1b was hydroboration reaction was investigated using differ-
obtained in 92% yield in the presence of 5.4 mol% Fe- ently substituted styrene derivatives, Fe-DOPA-Cu
DOPA-Cu NPs (based on Cu), 1.5 equiv. of B2pin2 and NPs (5.4 mol%, based on Cu), B2pin2 (1.5 equiv.),
KOtBu, 5 equiv. of MeOH as an additive in toluene at KOtBu (1.5 equiv.), and MeOH (5 equiv.) in DMF at
°
80 C (entry 1). We screened a range of solvents room temperature, as depicted in Table 2. Neutral (1a),
(entries 2–4); with DMF (dimethylformamide) provid- electron-donating substituents, such as p-Me (2a) and
ing 1b in 99% yield (entry 4). To our delight, 1b could m-OMe (3a) groups were well tolerated, affording the
be obtained in quantitative yield (89% isolated yield) desired primary alkylboronate esters in excellent
at room temperature (entry 5). Switching the catalyst yields. Reaction with electron-deficient 1-chloro-4-
to nano-Fe3O4 or nano-Fe3O4-DOPA gave lower yield vinylbenzene (4a) gave the alkylboronate ester 4b in
of 1b (entries 6 and 7). The reaction of 1a with B2pin2 82% yield. A nitrogen containing heteroaromatic
in DMF in the absence of a catalyst gave trace amount substrate 9-vinylcarbazole (6a) gave the desire product
of desire product (entry 8).[6j] Next, several bases were in moderate yield (54%). Subsequently, allyl benzene
screened; LiOtBu, NaOtBu, KOMe, and NaOMe (7a) efficiently gave phenylpropyl boronic ester (7b)
displayed poor reactivities (entries 9–12). When base in 86% yield. To our delight, sterically hindered 1,3,5-
was absent, no hydroborated product was detected by trimethyl-2-vinylbenzene (8a) was hydroborated in
GC-MS analysis (entry 13). Importantly, the reaction good yield. We tested the compatibility of 1,1-
can be performed in air, giving the desired 1b in 96% disubstituted terminal styrene (9a) under the standard
yield (entry 14).
conditions gave 9b in good yield. Our examination
Substrate scope. With the optimized protocol in also included an internal alkene, and the hydroboration
hand, the scope of the anti-Markovnikov-selective of trans-β-methylstyrene (10a) was converted into
Adv. Synth. Catal. 2021, 363, 2408–2416
2409
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
was obtained under standard reaction conditions. If
excess mercury (300 equiv.) was added after 8 h
reaction process, only 48% yield of 1b was observed.
These results confirmed the heterogeneity of the
catalytic system. Further catalyst filtration experiment
shows that metal leaching of the catalyst is negligible
during the reaction process. To show the efficacy of
this heterogeneous catalyst system, recycling experi-
ments were carried out. To our delight, quantitative
yield was obtained in the hydroboration of 1a using a
recycled Fe-DOPA-Cu NPs catalyst up to five
repeated runs with no considerable loss in the activity.
Next, we explored the possibility of a radical
mechanism by performing the reactions in the presence
of a radical scavengers 9,10-dihydroanthracene and
Table 2. Substrate scope of Fe-DOPA-Cu NPs catalyzed
hydroboration of alkenes.[a]
TEMPO
(2,2,6,6-tetramethyl-1-piperidinyloxy;
Scheme 1). In both cases, addition of radical inhibitor
shuts down the reaction almost completely, suggesting
that the hydroboration reaction seems to proceed via a
radical mechanism. Furthermore, radical clock reaction
was conducted using vinylcyclopentane (11a) as the
substrate under the standard conditions (Scheme 2).
The straightforward hydroboration product (11b) in
11% yield and cyclohexylmethyl-Bpin (11c) in 37%
1
yield were detected from the isolated mixture by H
NMR and GC-MS analysis (see SI for details). The
ring-opening product was not detected. The formation
of 11c, suggests an involvement of radical species in
the reaction.
When the hydroboration of 1a was performed with
HBpin (pinacolborane) under the standard conditions,
[a] Reaction conditions: Alkene (1.0 mmol, 1 equiv.), Fe-
DOPA-Cu NPs (100 mg), B2pin2 (1.5 equiv.), KOtBu
(1.5 equiv.), MeOH (5 equiv.), DMF, RT for 24 h unless
otherwise stated. Yields were determined by 1H NMR
spectroscopy using nitromethane as an internal standard.
Isolated yields are given in parentheses.
10b in 76% yield. However, linear aliphatic alkene 1-
octene provided mixture of hydroboration products
(see Supporting Information (SI) for details). Our
method is amenable to gram scale synthesis. The
hydroboration of 1a gave the desired product 1b in
86% yield (1.99 g). Further switching B2pin2 with bis
(neopentylglycolato)diboron (B2neop2),[21] giving the
corresponding 2-phenylethylÀ Bneop compound in
moderate yield (55%; see SI).
Next, to demonstrate the utility and the importance
of organoboron derivatives in organic synthesis, further
transformation of hydroboration product was carried
out. 1b was efficiently converted into corresponding
alcohol 1b–OH under mild oxidative conditions in
82% yield (see SI for detail).
Scheme 1. Radical scavenging experiments using: a) 9,10-
dihydroanthracene and b) TEMPO.
Mechanism studies. To investigate the heteroge-
neous nature of this Fe-DOPA-Cu NPs catalyzed
hydroboration reaction system, mercury poisoning
studies and filtration experiment were performed.
When the hydroboration of 1a was performed in the
presence of excess mercury (300 equiv.) along with the
catalyst at the beginning of the reaction, no product
Scheme 2. Hydroboration of vinylcyclopentane (11a).
Adv. Synth. Catal. 2021, 363, 2408–2416
2410
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
no desire product was observed, demonstrating that the
reaction did not involve the formation of HBpin
intermediate (see SI for details).[6j] Further the stoichio-
metric reaction mixture was monitored by 11B NMR
spectroscopy, there were no resonance of any boron-
containing species other than the product and B2pin2,
probably due to the paramagnetic nature of Cu(II).
Table 3. Optimization of reaction conditions for the Fe-
DOPA-Cu NPs catalyzed β-borylation of benzylideneacetophe-
none (12a).[a]
[b]
°
Entry Catalyst (NPs) Base
Solvent T ( C) Yield (%)
β-Borylation of α,β-Unsaturated Carbonyl Com-
pound
1
Cu2O
CuO
K2CO3 Toluene 60
K2CO3 Toluene 60
4
30
2
3
4
5
6
7
8
9
10
11
12
13
Fe-DOPA-Cu K2CO3 Toluene 60
Fe3O4 K2CO3 Toluene 60
Fe3O4-DOPA K2CO3 Toluene 60
– K2CO3 Toluene 60
Fe-DOPA-Cu Cs2CO3 Toluene 60
Fe-DOPA-Cu KOAc Toluene 60
92
The catalytic addition of a boronate group to α,β-
unsaturated carbonyl compounds at the β-position has
attracted much attention in recent years.[9] To date,
several homogeneous catalyst systems including Pd,[22]
Pt,[9a,d,23] Rh,[24] Ni,[25] Cu,[9b,c,26] and N-heterocyclic
carbenes[26f,27] have been developed for β-borylation of
α,β-unsaturated carbonyl compounds. These methods
provide useful tools to synthesis alkylboronate esters,
however, they also having some limitations such as
harsh conditions, high catalyst loading, expensive
ligands, and narrow substrate scope. Recently, tran-
sition-metal-free conjugate addition of α,β-unsaturated
Trace
Trace
0
21
42
36
51
75
15
Fe-DOPA-Cu –
Toluene 60
Fe-DOPA-Cu K2CO3 Hexane 60
Fe-DOPA-Cu K2CO3 Benzene 60
Fe-DOPA-Cu K2CO3 THF
60
Fe-DOPA-Cu K2CO3 Toluene RT
91
14[c] Fe-DOPA-Cu K2CO3 Toluene RT
96 (96)[d]
[a] Reaction conditions: 12a (0.25 mmol, 1 equiv.), Fe-DOPA-
Cu NPs (25 mg), base (10 mol%), B2pin2 (1.2 equiv.), solvent
°
carbonyl compounds at 70 C was also developed by
Song et al.[28a] There are few reports on recyclable
heterogeneous catalyst systems for β-borylation of
carbonyl compounds,[29] catalysts suitable for both the
hydroboration of alkenes and α,β-unsaturated carbonyl
°
(1 mL), MeOH (2 equiv.) for 12 h at 60 C unless otherwise
stated.
[b] Yields were determined by GC-MS analysis using n-
dodecene as an internal standard.
compounds are rare.[17b] Given the huge potential of [c] Reaction was performed for 18 h at room temperature.
[d] Isolated yield after chromatographic workup.
copper catalysis,[9k] we envisioned that the Fe-DOPA-
Cu NPs catalysis would be a feasible approach for the
introduction of a boronate group to α,β-unsaturated
carbonyl compounds.
obtained when the reaction was carried out for 18 h at
We started our investigation using benzylideneace- room temperature (96% yield, entry 14).
tophenone (12a) as the substrate and B2pin2 as the
Substrate scope of β-borylation of α,β-unsatu-
boron source (Table 3). Treatment of 12a with B2pin2 rated carbonyl compounds. With the optimum con-
using Cu2O NPs as catalyst and K2CO3 as the base and ditions in hand, the generality of the β-borylation was
°
methanol as an additive in toluene at 60 C for 12 h investigated by using Fe-DOPA-Cu NPs (5.4 mol%,
showed little conversion (entry 1). The use of CuO based on Cu), K2CO3 (10 mol%) in toluene and MeOH
NPs as catalyst yielded 12b in moderate yield (30%, (2.0 equiv.) as proton source for 18 h at room temper-
entry 2). With Fe-DOPA-Cu NPs as catalyst the ature (Table 4). The Fe-DOPA-Cu NPs catalyzes the
corresponding alkylboronate ester 12b was formed in β-borylation of a variety of α,β-unsaturated carbonyl
good yield (92%, entry 3), while Fe3O4 NPs and Fe3O4- compounds efficiently with B2pin2. The reactions of
DOPA (entries 4 and 5) provided trace amounts of chalcones having electron-withdrawing (13a–16a) and
12b. In the absence of catalyst, only a trace amount of electron-donating (17a–19a) substituents gave the
desired product was obtained; thus, any uncatalyzed desire boronates in excellent yields (85–98%). Sub-
reaction is minimal (entry 6). Next, the base effect was strates containing both electron-withdrawing and -do-
tested. Bases Cs2CO3 and KOAc were proved inferior nating groups afforded good to excellent yield of
(entries 7 and 8). In the absence of base, lower yield of desired products (20b and 21b). Further, the β-
β-borylation product was observed by GC-MS analysis borylation of methyl cinnamate (22a) and cinnamalde-
(entry 9). We also test the effect of solvents. With hyde (23a) gave the corresponding addition products
hexane and benzene as solvent, the desired products 22b in 98% yield and 23b in 64% yield. The process
were obtained in lower yields (entries 10 and 11). allows convenient gram scale synthesis (5 mmol) with
Reaction in THF resulted in limited reaction (entry 12). the same efficiency, as demonstrated for 12a (12b:
To our delight, when the reaction was performed at 1.48 g, 88%).
room temperature afforded yield comparable to those
Mechanistic investigations. Mercury poisoning
°
for at 60 C (91%, entry 13). Excellent yield was studies were conducted to prove that the Fe-DOPA-Cu
Adv. Synth. Catal. 2021, 363, 2408–2416
2411
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
Table 4. Substrate scope of Fe-DOPA-Cu NPs catalyzed β-
borylation of α,β-unsaturated carbonyl compounds.[a]
Scheme 4. Hydrogen isotope-labelling experiment.
continuation of the reaction. These results suggest
negligible metal leaching of the catalyst during the
reaction process, which support the excellent stability
of the Fe-DOPA-Cu NPs catalyst.
In order to study the recyclability of the NPs
catalyst, β-borylation of benzylideneacetophenone
(12a) with B2pin2 was examined under standard
reaction protocol. Gratifyingly, catalyst is recyclable
and reusable up to five consecutive cycles without loss
of activity. The recycling experiment was performed
by applying an external magnet to recover the catalyst
after each run, washing with solvent and drying in the
°
oven at 60 C for 4 h.
To understand the origin of the hydrogen source of
the β-borylation product, isotope-labelling experiment
was performed (Scheme 4). The β-borylation of
chalcone 12a was carried out using CD3OD as an
additive instead of CH3OH under the standard con-
ditions. The result revealed 82% of the deuterated β-
borylation product 12b–D (of which ca. 55% was
deuterated), determined by GC-MS analysis, indicated
that the CD3OD served as the hydrogen source in this
borylation reaction.
[a] Reaction conditions: α,β-unsaturated carbonyl compound
(1.0 mmol, 1 equiv.), Fe-DOPA-Cu NPs (100 mg), B2pin2
(1.2 equiv.), K2CO3 (10 mol%), MeOH (2 equiv.), toluene
(4 mL), RT for 18 h unless otherwise stated (see SI for
detail). Yields are of isolated products.
[b]
°
Reaction was performed at 60 C.
[c] Yield was determined by 1H NMR spectroscopy using
nitromethane as an internal standard.
Conclusion
NPs is the true catalyst (Scheme 3). These experiments
confirmed the heterogeneity of the catalytic system. In In conclusion, we have developed efficient, magneti-
a filtration experiment, the Fe-DOPA-Cu NPs catalyst cally separable, and easily recyclable Cu nano-catalysts
was filtered off after the 8 h reaction progress, and the for the hydroboration of alkenes and β-borylation of
filtrate reaction mixture was stirred at room temper- α,β-unsaturated ketones and ester with diboron re-
ature for the next 4 hours under standard reaction agents, under mild reaction conditions. These methods
conditions. Interestingly, after the removal of the tolerate a variety of functional groups, providing easy
catalyst no yield enhancement of 12b was observed, access to the corresponding alkylboronate esters in
further addition of the removed catalyst led to good yields. Further studies on nanoparticles catalyzed
diverse unsaturated organic substrates borylation func-
tionalization and related mechanism are under way.
Experimental Section
General Information and Chemicals
All reagents were purchased from TCI, SDFCL or Aldrich and
were used as received. CDCl3 were purchased from Cambridge
Isotope Laboratories and were dried using molecular sieves and
deoxygenated using the freeze-pump-thaw method. All NMR
spectra were recorded at ambient temperature using a Bruker
Avance 400 NMR spectrometer (1H, 400 MHz; 13C, 100 MHz;
11B, 128 MHz). 1H NMR chemical shifts are reported relative to
Scheme 3. a) β-Borylation of 12a in the presence of mercury
with Fe-DOPA-Cu NPs catalyst. b) Addition of mercury after
8 h reaction progress.
TMS and were referenced via residual proton resonances of the
corresponding deuterated solvent (CDCl3: 7.26 ppm) whereas
Adv. Synth. Catal. 2021, 363, 2408–2416
2412
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
13C NMR spectra are reported relative to TMS using the carbon
signals of the deuterated solvent (CDCl3: 77.16 ppm). 11B NMR
signals were quoted relative to BF3 ·Et2O. All 11B and 13C NMR
Experimental Procedure for Examples Described in
Table 3
1
In a 10 mL thick-walled reaction tube equipped with a magnetic
stirring bar, Fe-DOPA-Cu NPs catalyst (25 mg; 5.4 mol%
based on Cu), B2pin2 (0.3 mmol), base (10 mol%), MeOH
spectra were broad-band H decoupled. The IR spectra were
obtained with a BRUKER ALPHA spectrometer in the range of
400 to 4000 cmÀ 1 using KBr windows. GC-MS data were
acquired using SHIMADZU GC-MS QP 2010SE system.
HRMS data were obtained using Agilent 6538 ultra high
definition (UHD) system using positive ion mode.
(2 equiv.,
0.5 mmol),
benzylideneacetophenone
(12a,
0.25 mmol) and solvent (1 mL) were added. The reaction
mixture was stirred for the indicated amount of time. The crude
reaction mixture was diluted with Et2O (2 mL) and filtered
through a plug of celite (∅ 3 mm×8 mm) and concentrated. In
the concentrated crude reaction mixture n-dodecene was added
as an internal standard. The product yield was determined by
GC-MS analysis using n-dodecene as an internal standard.
The microstructure of the nanoparticle was studied by Rigaku
Ultima IV powder XÀ-r1ay diffractometer using Cu Kα radiation
°
(scan rate of 3 min ). Scanning electron microscopy (SEM)
and energy-dispersive X-ray spectroscopic (EDX) spectra were
performed on a JSM 7100F JEOL FESEM with EDS, and TEM
was carried out using JEOL transmission electron microscope
operating at 200 kV after casting a drop of nanoparticle
dispersion in isopropyl alcohol over Cu grid. ICP-MS data were
obtained with a Thermo Scientific™ iCAP Q ICP-MS. X-ray
photoelectron spectroscopy was carried out on Axis Ultra DLD.
Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda
(BJH) measurements were carried out on BELSORP-max
instrument. Fe-DOPA-Cu NP was prepared according to the
literature.[19a,20]
Experimental Procedure for Examples Described in
Table 4
In a 25 mL thick-walled reaction tube equipped with a magnetic
stirring bar, Fe-DOPA-Cu NPs (100 mg, 5.4 mol% of Cu),
B2pin2 (1.2 equiv., 305 mg, 1.2 mmol), K2CO3 (10 mol%,
14 mg, 0.1 mmol), toluene (4 mL), MeOH (2 equiv., 80 μL,
2 mmol) and α,β-unsaturated carbonyl compound (1 mmol)
were added and the reaction was stirred vigorously at room
temperature for 18 h. The reaction mixture was then diluted
with EtOAc (8 mL) and filtered through a plug of celite (∅
3 mm×8 mm) with copious washing (EtOAc). The solvents
were removed in vacuo, and the residue was purified by column
chromatography.
General Procedure for Examples Described in
Table 1
In a 10 mL thick-walled reaction tube equipped with a magnetic
stirring bar, Fe-DOPA-Cu NPs catalyst (25 mg; 5.4 mol%
based on Cu), B2pin2 (0.37 mmol), base (0.37 mmol), MeOH
(5 equiv., 1.25 mmol), styrene (1a, 0.25 mmol), and solvent
(1 mL) were added. The reaction mixture was stirred at room
temperature for the indicated amount of time. The crude
reaction was dissolved in Et2O (10 mL) and then transferred to
a separatory funnel followed by the addition of H2O (10 mL).
The layers were separated, and the organic layer was washed
once with brine. The combined aqueous layers were further
extracted with Et2O (3×5 mL). The combined organics were
dried (Na2SO4) and concentrated. In the concentrated crude
reaction mixture nitromethane was added as an internal
standard. The product yield was determined by 1H NMR
spectroscopy using nitromethane as an internal standard.
Acknowledgements
S.K.B. thanks SERB (EMR/2017/000844) and JAIN (Deemed-
to-be University) start-up research grant, for funding. The
authors also thank AllyChem Co. Ltd. for a generous gift of
B2pin2 and B2neop2, the Nanomission (SR/NM/NS-20/2014) for
providing FESEM, EDX and PXRD analysis, IISc for NMR,
XPS and 200 kV FETEM facilities. We thank Ms. Swavalina
Baruah and Ms. Sheema Siddiqui for their help in obtaining the
NMR and HRMS data.
References
Experimental Procedure for Examples Described in
Table 2
[1] a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457–
2483; b) S. R. Chemler, D. Trauner, S. J. Danishefsky,
Angew. Chem. Int. Ed. 2001, 40, 4544–4568; Angew.
Chem. 2001, 113, 4676; c) S. Darses, J. P. Genet, Chem.
Rev. 2008, 108, 288–325; d) Boronic Acids-Preparation
and Applications in Organic Synthesis, Medicine and
Materials. 2nd ed.; Wiley-VCH: Weinheim: 2011; e) R.
Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111,
1417–1492; f) T. S. De Vries, A. Prokofjevs, E. Vedejs,
Chem. Rev. 2012, 112, 4246–4282; g) E. Dimitrijević,
M. S. Taylor, ACS Catal. 2013, 3, 945–962; h) Z. He, A.
Zajdlik, A. K. Yudin, Dalton Trans. 2014, 43, 11434–
11451; i) A. J. J. Lennox, G. C. Lloyd-Jones, Chem. Soc.
Rev. 2014, 43, 412–443; j) L. Xu, S. Zhang, P. Li, Chem.
Soc. Rev. 2015, 44, 8848–8858; k) E. C. Neeve, S. J.
In a 25 mL thick-walled reaction tube equipped with a magnetic
stirring bar, Fe-DOPA-Cu NPs (100 mg, 5.4 mol% of Cu),
B2pin2 (1.5 equiv., 381 mg, 1.5 mmol), KOtBu (1.5 equiv.,
168 mg, 1.5 mmol), DMF (6 mL), MeOH (5 equiv., 200 μL,
5 mmol), and alkene (a, 1 mmol) were added, and the reaction
was stirred vigorously at room temperature for 24 h. The crude
reaction mixture was dissolved in Et2O (30 mL) and then
transferred to a separatory funnel followed by the addition of
H2O (30 mL). The layers were separated, and the organic layer
was washed once with brine. The combined aqueous layers
were further extracted with Et2O (3 x 10 mL). The combined
organics were dried (Na2SO4) and concentrated. The residue
was purified by column chromatography.
Adv. Synth. Catal. 2021, 363, 2408–2416
2413
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
Geier, I. A. I. Mkhalid, S. A. Westcott, T. B. Marder,
Chem. Rev. 2016, 116, 9091–9161; l) H. Yoshida, ACS
Catal. 2016, 6, 1799–1811; m) J. W. B. Fyfe, A. J. B.
Watson, Chem. 2017, 3, 31–55; n) L. Xu, G. Wang, S.
Zhang, H. Wang, L. Wang, L. Liu, J. Jiao, P. Li,
Tetrahedron 2017, 73, 7123–7157; o) K. Geetharani,
S. K. Bose, in Science of Synthesis: Advances in Organo-
boron Chemistry towards Organic Synthesis, (Ed. E.
Fernández), Thieme: Stuttgart, 2019, pp 335–354;
p) A. B. Cuenca, R. Shishido, H. Ito, E. Fernández,
Chem. Soc. Rev. 2017, 46, 415–430; q) K. Kubota, H.
Iwamoto, H. Ito, Org. Biomol. Chem. 2017, 15, 285–300;
r) Y.-M. Tian, X.-N. Guo, H. Braunschweig, U. Radius,
T. B. Marder, Chem. Rev. 2021, DOI: 10.1021/acs.chem-
rev.0c01236.
and Palladium-Catalyzed Asymmetric Conjugate Addi-
tion of Organoboronic Acid, 2nd ed. (Ed.: D. G. Hall),
Wiley-VCH, Weinheim, 2011, pp. 263–314; d) A.
Suzuki, Angew. Chem. Int. Ed. 2011, 50, 6722–6737;
Angew. Chem. 2011, 123, 6854–6869; e) N. Miyaura, in
Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.
(Ed.: A. D. Meijere), Wiley-VCH: Weinheim, Germany,
2004, pp. 41–123; f) N. Miyaura, Bull. Chem. Soc. Jpn.
2008, 81, 1535–1553; g) G. A. Molander, B. Canturk,
Angew. Chem. Int. Ed. 2009, 48, 9240–9261; Angew.
Chem. 2009, 121, 9404–9425; h) D. V. Partyka, Chem.
Rev. 2011, 111, 1529–1595.
[5] a) H. C. Brown, Organic Syntheses via Boranes, Wiley,
New York, 1975; b) A. A. Desai, Angew. Chem. Int. Ed.
2012, 51, 9223–9225; Angew. Chem. 2012, 124, 9357–
9359.
[2] a) L. Borissenko, M. Groll, Chem. Rev. 2007, 107, 687–
717; b) J. Adams, M. Behnke, S. Chen, A. A. Cruick-
shank, L. R. Dick, L. Grenier, J. M. Klunder, Y.-T. Ma,
L. Plamondon, R. L. Stein, Bioorg. Med. Chem. Lett.
1998, 8, 333–338; c) A. Paramore, S. Frantz, Nat. Rev.
Drug Discov. 2003, 2, 611–612; d) A. S. Ivanov, A. A.
Zhalnina, S. V. Shishkov, Tetrahedron 2009, 65, 7105–
7108; e) J. Adams, M. Kauffman, Cancer Invest. 2004,
22, 304–311; f) P. Moreau, T. Masszi, N. Grzasko, N. J.
Bahlis, M. Hansson, L. Pour, I. Sandhu, P. Ganly, B. W.
Baker, S. R. Jackson, A. M. Stoppa, D. R. Simpson, P.
Gimsing, A. Palumbo, L. Garderet, M. Cavo, S. Kumar,
C. Touzeau, F. K. Buadi, J. P. Laubach, D. T. Berg, J.
Lin, A. Di Bacco, A. M. Hui, H. van de Velde, P. G.
Richardson, T.-M. S. Group, New Engl. J. Med. 2016,
374, 1621–1634; g) L. J. Milo, J. H. Lai Jr, W. Wu, Y.
Liu, H. Maw, Y. Li, Z. Jin, Y. Shu, S. E. Poplawski, Y.
Wu, D. G. Sanford, J. L. Sudmeier, W. W. Bachovchin, J.
Med. Chem. 2011, 54, 4365–4377; h) M. A. Beenen, C.
An, J. A. Ellman, J. Am. Chem. Soc. 2008, 130, 6910–
6911.
[3] a) C. D. Entwistle, T. B. Marder, Angew. Chem. Int. Ed.
2002, 41, 2927–2931; Angew. Chem. 2002, 114, 3051–
3056; b) C. D. Entwistle, T. B. Marder, Chem. Mater.
2004, 16, 4574–4585; c) S. Yamaguchi, A. Wakamiya,
Pure Appl. Chem. 2006, 78, 1413–1424; d) M. Elbing,
G. C. Bazan, Angew. Chem. Int. Ed. 2008, 47, 834–838;
Angew. Chem. 2008, 120, 846–850; e) A. Fukazawa, S.
Yamaguchi, Chem. Asian J. 2009, 4, 1386–1400; f) F.
Jäkle, Chem. Rev. 2010, 110, 3985–4022; g) Y. L. Rao,
H. Amarne, S. Wang, Coord. Chem. Rev. 2012, 256,
759–770; h) A. Lorbach, A. Hübner, M. Wagner, Dalton
Trans. 2012, 41, 6048–6063; i) A. Wakamiya, S.
Yamaguchi, Bull. Chem. Soc. Jpn. 2015, 88, 1357–1377;
j) S. Mukherjee, P. Thilagar, J. Mater. Chem. C 2016, 4,
2647–2662; k) H. Helten, Chem. Eur. J. 2016, 22,
12972–12982; l) Y. Ren, F. Jäkle, Dalton Trans. 2016,
45, 13996–14007; m) L. Ji, S. Griesbeck, T. B. Marder,
Chem. Sci. 2017, 8, 846–863.
[6] a) D. Männig, H. Nöth, Angew. Chem. Int. Ed. Engl.
1985, 24, 878–879; Angew. Chem. 1985, 97, 854–855;
b) K. Burgess, W. A. van der Donk, S. A. Westcott, T. B.
Marder, R. T. Baker, J. C. Calabrese, J. Am. Chem. Soc.
1992, 114, 9350–9359; c) D. A. Evans, G. C. Fu, A. H.
Hoveyda, J. Am. Chem. Soc. 1992, 114, 6671–6679;
d) D. R. Edwards, C. M. Crudden, K. Yam, Adv. Synth.
Catal. 2005, 347, 50–54; e) G. C. Fu, in Transition
Metal-Catalyzed Hydroboration of Olefins, Transition
Metals for Organic Synthesis: Building Blocks and Fine
Chemicals, 2nd ed. (Eds.: M. Beller, C. Bolm), Wiley-
VCH, Weinheim, 2008, 193–198; f) A. Whiting, J.-B.
Chen, Synthesis 2018, 50, 3843–3861; g) J. D. Hewes,
C. W. Kreimendahl, T. B. Marder, M. F. Hawthorne, J.
Am. Chem. Soc. 1984, 106, 5757–5759; h) K. Burgess,
W. A. Van der Donk, S. A. Westcott, T. B. Marder, R. T.
Baker, J. C. Calabrese, J. Am. Chem. Soc. 1992, 114,
9350–9359; i) W. Fan, L. Li, G. Zhang, J. Org. Chem.
2019, 84, 5987–5996; j) A. D. Bage, K. Nicholson, T. A.
Hunt, T. Langer, S. P. Thomas, ACS Catal. 2020, 10,
13479–13486.
[7] a) I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M.
Murphy, J. F. Hartwig, Chem. Rev. 2010, 110, 890–931;
b) J. F. Hartwig, Acc. Chem. Res. 2012, 45, 864–873;
c) J. F. Hartwig, Chem. Soc. Rev. 2011, 40, 1992–2002;
d) J. F. Hartwig, J. Am. Chem. Soc. 2016, 138, 2–24;
e) T. Ishiyama, N. Miyaura, J. Organomet. Chem. 2003,
680, 3–11; f) J. Kalepu, L. T. Pilarski, Molecules 2019,
24, 830; g) A. Ros, R. Fernández, J. M. Lassaletta,
Chem. Soc. Rev. 2014, 43, 3229–3243; h) H. Chen, S.
Schlecht, T. C. Semple, J. F. Hartwig, Science 2000, 287,
1995–1997; i) H. Chen, J. F. Hartwig, Angew. Chem. Int.
Ed. 1999, 38, 3391–3393; Angew. Chem. 1999, 111,
3597.
[8] a) C.-T. Yang, Z.-Q. Zhang, H. Tajuddin, C.-C. Wu, J.
Liang, J.-H. Liu, Y. Fu, M. Czyzewska, P. G. Steel, T. B.
Marder, L. Liu, Angew. Chem. Int. Ed. 2012, 51, 528–
532; Angew. Chem. 2012, 124, 543–547; b) H. Ito, K.
Kubota, Org. Lett. 2012, 14, 890–893; c) K. Kubota, E.
Yamamoto, H. Ito, J. Am. Chem. Soc. 2013, 135, 2635–
2640; d) H. Iwamoto, K. Kubota, E. Yamamoto, H. Ito,
Chem. Commun. 2015, 51, 9655–9658; e) J. H. Kim,
[4] a) N. R. Candeias, F. Montalbano, P. M. S. D. Cal,
P. M. P. Gois, Chem. Rev. 2010, 110, 6169–6193; b) J. X.
Qiao, P. Y. S. Lam, Synthesis 2011, 829–856; c) G.
Berthon-Gelloz, T. Hayashi in Boronic Acids. Rhodium-
Adv. Synth. Catal. 2021, 363, 2408–2416
2414
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
Y. K. Chung, RSC Adv. 2014, 4, 39755–39758; f) X.-F.
Zhou, Y.-D. Wu, J.-J. Dai, Y.-J. Li, Y. Huang, H.-J. Xu,
2, 42–46; r) Y. Yamamoto, T. Nishikata, N. Miyaura,
Pure Appl. Chem. 2008, 80, 807–817.
RSC Adv. 2015, 5, 46672–46676; g) A. S. Dudnik, G. C. [10] For reviews on precious-metal-catalyzed hydroboration
Fu, J. Am. Chem. Soc. 2012, 134, 10693–10697; h) J. Yi,
J.-H. Liu, J. Liang, J.-J. Dai, C.-T. Yang, Y. Fu, L. Liu,
Adv. Synth. Catal. 2012, 354, 1685–1691; i) M. S.
Cheung, F. K. Sheong, T. B. Marder, Z. Lin, Chem. Eur.
J. 2015, 21, 7480–7488; j) A. Joshi-Pangu, X. Ma, M.
Diane, S. Iqbal, R. J. Kribs, R. Huang, C.-Y. Wang,
M. R. J. Biscoe, J. Org. Chem. 2012, 77, 6629–6633;
reactions, see: a) K. Burgess, M. J. Ohlmeyer, Chem.
Rev. 1991, 91, 1179–1191; b) I. Beletskaya, A. Pelter,
Tetrahedron 1997, 53, 4957–5026; c) C. M. Crudden, D.
Edwards, Eur. J. Org. Chem. 2003, 4695–4712; d) A.-M.
Carroll, T. P. O’Sullivan, P. J. Guiry, Adv. Synth. Catal.
2005, 347, 609–631; e) C. M. Vogels, S. A. Westcott,
Curr. Org. Chem. 2005, 9, 687–699.
k) T. C. Atack, R. M. Lecker, S. P. J. Cook, J. Am. Chem. [11] For reviews on first-row-transition-metal-catalyzed hy-
2014, 136, 9521–9523; l) R. B. Bedford, P. B. Brenner,
E. Carter, T. Gallagher, D. M. Murphy, D. R. Pye,
Organometallics 2014, 33, 5940–5943; m) S. K. Bose,
K. Fucke, L. Liu, P. G. Steel, T. B. Marder, Angew.
Chem. Int. Ed. 2014, 53, 1799–1803; Angew. Chem.
2014, 126, 1829–1834; n) S. K. Bose, T. B. Marder, Org.
Lett. 2014, 16, 4562–4565; o) S. K. Bose, A.
Deißenberger, A. Eichhorn, P. G. Steel, Z. Lin, T. B.
droboration reactions, see: a) J. A. Schiffner, K. Müther,
M. Oestreich, Angew. Chem. Int. Ed. 2010, 49, 1194–
1196; Angew. Chem. 2010, 122, 1214–1216; b) J. A.
Bull, Angew. Chem. Int. Ed. 2012, 51, 8930–8932;
Angew. Chem. 2012, 124, 9060–9062; c) W. Fan, L. Li,
G. Zhang, J. Org. Chem. 2019, 84, 5987–5996; d) J. V.
Obligacion, P. J. Chirik, Nature Rev. Chem. 2018, 2, 15–
34.
Marder, Angew. Chem. Int. Ed. 2015, 54, 11843–11847; [12] a) D. Noh, H. Chea, J. Ju, J. Yun, Angew. Chem. Int. Ed.
Angew. Chem. 2015, 127, 12009–12014; p) T. C. Atack,
S. P. Cook, J. Am. Chem. Soc. 2016, 138, 6139–6142;
q) S. K. Bose, S. Brand, H. O. Omoregie, M. Haehnel, J.
Maier, G. Bringmann, T. B. Marder, ACS Catal. 2016, 6,
8332–8335; r) H. Iwamoto, S. Akiyama, K. Hayama, H.
Ito, Org. Lett. 2017, 19, 2614–2617.
2009, 48, 6062–6064; Angew. Chem. 2009, 121, 6178–
6180; b) D. Noh, S. K. Yoon, J. Won, J. Y. Lee, J. Yun,
Chem. Asian J. 2011, 6, 1967–1969; c) S. C. Schmid, R.
Van Hoveln, J. W. Rigoli, J. M. Schomaker, Organo-
metallics 2015, 34, 4164–4173; d) H. A. Kerchner, J.
Montgomery, Org. Lett. 2016, 18, 5760–5763.
[9] a) Y. G. Lawson, M. J. G. Lesley, N. C. Norman, C. R. [13] a) J. V. Obligacion, P. J. Chirik, J. Am. Chem. Soc. 2013,
Rice, T. B. Marder, Chem. Commun. 1997, 2051–2052;
b) K. Takahashi, T. Ishiyama, N. Miyaura, Chem. Lett.
2000, 29, 982–983; c) H. Ito, H. Yamanaka, J. Tateiwa,
A. Hosomi, Tetrahedron Lett. 2000, 41, 6821–6825;
d) N. J. Bell, A. J. Cox, N. R. Cameron, J. S. O. Evans,
T. B. Marder, M. A. Duin, C. J. Elsevier, X. Baucherel,
135, 19107–19110; b) L. Zhang, Z. Zuo, X. Leng, Z.
Huang, Angew. Chem. Int. Ed. 2014, 53, 2696–2700;
Angew. Chem. 2014, 126, 2734–2738; c) L. Zhang, Z.
Zuo, X. Wan, Z. Huang, J. Am. Chem. Soc. 2014, 136,
15501–15504; d) W. N. Palmer, T. Diao, I. Pappas, P. J.
Chirik, ACS Catal. 2015, 5, 622–626.
A. A. D. Tulloch, R. P. Tooze, Chem. Commun. 2004, [14] a) J. Y. Wu, B. Moreau, T. Ritter, J. Am. Chem. Soc.
1854–1855; e) L. Dang, Z. Lin, T. B. Marder, Organo-
metallics 2008, 27, 4443–4454; f) H. Wu, S. Radomkit,
J. M. O’Brien, A. H. Hoveyda, J. Am. Chem. Soc. 2012,
134, 8277–8285; g) E. Hartmann, D. J. Vyas, M.
Oestreich, Chem. Commun. 2011, 47, 7917–7932; h) Y.
Sasaki, Y. Horita, C. Zhong, M. Sawamura, H. Ito,
Angew. Chem. Int. Ed. 2011, 50, 2778–2782; Angew.
2009, 131, 12915–12917; b) J. V. Obligacion, P. J.
Chirik, Org. Lett. 2013, 15, 2680–2683; c) L. Zhang, D.
Peng, X. Leng, Z. Huang, Angew. Chem. Int. Ed. 2013,
52, 3676–3680; Angew. Chem. 2013, 125, 3764–3768;
d) J. Zheng, J.-B. Sortais, C. Darcel, ChemCatChem
2014, 6, 763–766; e) J. Chen, T. Xi, Z. Lu, Org. Lett.
2014, 16, 6452–6455.
Chem. 2011, 123, 2830–2834; i) B. Liu, M. Gao, L. [15] a) G. Zhang, H. Zeng, J. Wu, Z. Yin, S. Zheng, J. C.
Dang, H. Zhao, T. B. Marder, Z. Lin, Organometallics
2012, 31, 3410–3425; j) J. Cid, H. Gulyás, J. J. Carbó, E.
Fernández, Chem. Soc. Rev. 2012, 41, 3558–3570; k) D.
Hemming, R. Fritzemeier, S. A. Westcott, W. L. Santos,
P. G. Steel, Chem. Soc. Rev. 2018, 47, 7477–7494; l) G.
Fettinger, Angew. Chem. Int. Ed. 2016, 55, 14369–
14372; Angew. Chem. 2016, 128, 14581–14584; b) J. R.
Carney, B. R. Dillon, L. Campbell, S. P. Thomas, Angew.
Chem. Int. Ed. 2018, 57, 10620–10624; Angew. Chem.
2018, 130, 10780–10784.
Stavber, Z. Časar, ChemCatChem 2014, 6, 2162–2174; [16] P. K. Verma, M. L. Shegavi, S. K. Bose, K. Geetharani,
m) V. Lillo, A. Bonet, E. Fernández, Dalton Trans. 2009, Org. Biomol. Chem. 2018, 16, 857–873.
2899–2908; n) B. S. L. Collins, C. M. Wilson, E. L. [17] a) S. Furukawa, M. Ieda, K.-I. Shimizu, ACS Catal.
Myers, V. K. Aggarwal, Angew. Chem. Int. Ed. 2017, 56,
11700–11733; Angew. Chem. 2017, 129, 11860–11894;
o) F. Beltran, E. Bergamaschi, I. Funes-Ardoiz, C. J.
Teskey, Angew. Chem. Int. Ed. 2020, 59, 21176–21182;
Angew. Chem. 2020, 132, 2–9; p) C. C. Chong, R. Kinjo,
ACS Catal. 2015, 5, 3238–3259; q) J.-B. Xie, S. Lin, J.
Luo, J. Wu, T. R. Winna, G. Li, Org. Chem. Front. 2015,
2019, 9, 5096–5103; b) R. Cano, D. J. Ramón, M. Yus,
J. Org. Chem. 2010, 75, 3458–3460; c) G. Zhang, J. Wu,
S. Li, S. Cass, S. Zheng, Org. Lett. 2018, 20, 7893–7897;
d) Y. Zhu, S. H. Agnes Jang, Y. H. Tham, O. B. Algin,
J. A. Maguire, N. S. Hosmane, Organometallics 2012,
31, 2589–2596; e) S. Hong, M. Liu, W. Zhang, Q. Zeng,
W. Deng, Tetrahedron Lett. 2015, 56, 2297–2302.
Adv. Synth. Catal. 2021, 363, 2408–2416
2415
© 2021 Wiley-VCH GmbH

FULL PAPER
asc.wiley-vch.de
[18] a) B. Mohan, K. H. Park, Appl. Catal. A 2016, 519, 78– [25] a) K. Hirano, H. Yorimitsu, K. Oshima, Org. Lett. 2007,
84; b) S. Thoka, M. Madasu, C.-F. Hsia, S.-Y. Liu, M. H.
Huang, Chem. Asian J. 2017, 12, 2318–2322; c) J. Zhao,
Z. Niu, H. Fu, Y. Li, Chem. Commun. 2014, 50, 2058–
2060; d) A. Grirrane, A. Corma, H. Garcia, Chem. Eur.
9, 5031–5033; b) Y. Sumida, H. Yorimitsu, K. Oshima,
J. Org. Chem. 2009, 74, 3196–3198; c) V. Lillo, M. J.
Geier, S. A. Westcott, E. Fernández, Org. Biomol. Chem.
2009, 7, 4674–4676.
J. 2011, 17, 2467–2478; e) C. Zhang, M. Zhou, S. Liu, [26] a) S. Mun, J.-E. Lee, J. Yun, Org. Lett. 2006, 8, 4887–
B. Wang, Z. Mao, H. Xu, Y. Zhong, L. Zhang, B. Xu, X.
Sui, Carbohydr. Polym. 2018, 191, 17–24; f) X. Zeng, C.
Gong, H. Guo, H. Xu, J. Zhang, J. Xie, New J. Chem.
2018, 42, 17346–17350.
4889; b) K. Takahashi, T. Ishiyama, N. Miyaura, J.
Organomet. Chem. 2001, 625, 47–53; c) J.-E. Lee, J.
Yun, Angew. Chem. Int. Ed. 2007, 47, 145–147; Angew.
Chem. 2008, 120, 151–153; d) J. M. O’Brien, K.-S. Lee,
A. H. Hoveyda, J. Am. Chem. Soc. 2010, 132, 10630–
10633; e) L. Zhao, Y. Ma, W. Duan, F. He, J. Chen, C.
Song, Org. Lett. 2012, 14, 5780–5783; f) L. Wang, Z.
Chen, M. Ma, W. Duan, C. Song, Y. Ma, Org. Biomol.
Chem. 2015, 13, 10691–10698; g) J.-E. Lee, J. Kwon, J.
Yun, Chem. Commun. 2008, 6, 733–734; h) H. Chea, H.-
S. Sim, J. Yun, Adv. Synth. Catal. 2009, 351, 855–858;
i) M. Gao, S. B. Thorpe, W. L. Santos, Org. Lett. 2009,
11, 3478–3481; j) H. Chea, H.-S. Sim, J. Yun, Bull.
Korean Chem. Soc. 2010, 31, 551–552; k) Q.-D. Wang,
J.-M. Yang, D. Fang, J. Ren, B. Dong, B. Zhou, B.-B.
Zeng, Tetrahedron Lett. 2016, 57, 2587–2590.
[19] a) M. L. Shegavi, A. Agarwal, S. K. Bose, Green Chem.
2020, 22, 2799–2803; b) M. L. Shegavi, S. K. Bose,
Catal. Sci. Technol. 2019, 9, 3307–3336; c) M. L.
Shegavi, A. Baishya, K. Geetharani, S. K. Bose, Org.
Chem. Front. 2018, 5, 3520–3525.
[20] R. B. Nasir Baig, R. S. Varma, Chem. Commun. 2012,
48, 2582–2584.
[21] a) P. Nguyen, G. Lesley, N. J. Taylor, T. B. Marder, N. L.
Picket, W. Clegg, M. R. J. Elsegood, N. C. Norman,
Inorg. Chem. 1994, 33, 4623–4624; b) F. J. Lawlor,
N. C. Norman, N. L. Pickett, E. G. Robins, P. Nguyen, G.
Lesley, T. B. Marder, J. A. Ashmore, J. C. Green, Inorg.
Chem. 1998, 37, 5282–5288.
[22] a) N. F. Pelz, A. R. Woodward, H. E. Burks, J. D. Sieber,
J. P. Morken, J. Am. Chem. Soc. 2004, 126, 16328–
16329; b) A. Bonet, H. Gulyás, I. O. Koshevoy, F.
[27] a) K. Lee, A. R. Zhugralin, A. H. Hoveyda, J. Am.
Chem. Soc. 2009, 131, 7253–7255; b) Z. Niu, J. Chen, Z.
Chen, M. Ma, C. Song, Y. Ma, J. Org. Chem. 2015, 80,
602–608.
Estevan, M. Sanaú, M. A. Úbeda, E. Fernández, Chem. [28] a) X. Huang, J. Hu, M. Wu, J. Wang, Y. Peng, G. Song,
Eur. J. 2010, 16, 6382–6390.
[23] H. A. Ali, I. Goldberg, M. Srebnik, Organometallics
2001, 20, 3962–3965.
Green Chem. 2018, 20, 255–260; b) X. Huang, M.
Wang, M. Wu, J. Wang, Y. Peng, G. Song, ChemistrySe-
lect 2017, 2, 1381–1385.
[24] a) G. W. Kabalka, B. C. Das, S. Das, Tetrahedron Lett. [29] a) Q. Yao, X. Lu, K. Liu, C. Ma, J. Su, C. Lin, D. Li, J.
2002, 43, 2323–2325; b) J. B. Morgan, S. P. Miller, J. P.
Morken, J. Am. Chem. Soc. 2003, 125, 8702–8703; c) T.
Shiomi, T. Adachi, K. Toribatake, L. Zhou, H. Nishiya-
ma, Chem. Commun. 2009, 40, 5987–5989.
Dou, J. Sun, W. Duan, Dalton Trans. 2019, 48, 5144–
5148; b) X.-F. Zhou, Y.-Y. Sun, Y.-D. Wu, J.-J. Dai, J.
Xu, Y. Huang, H.-J. Xu, Tetrahedron 2016, 72, 5691–
5698.
Adv. Synth. Catal. 2021, 363, 2408–2416
2416
© 2021 Wiley-VCH GmbH