Lithium Bromide/HBpin: A Mild and Effective Catalytic System for the Selective Hydroboration of Aldehydes and Ketones

Article abstract of DOI:10.1002/bkcs.12103

The catalytic hydroboration of aldehydes and ketones with HBpin was examined using simple and commercially available metal salts (Li, Na, and K). Among the tested salts, LiBr (0.5–1.0 mol%) was found to be an efficient catalyst for the hydroboration of various aldehydes and ketones at room temperature. Further, the chemoselective hydroboration of aldehydes over ketones was also demonstrated.

Full text of DOI:10.1002/bkcs.12103

Article
DOI: 10.1002/bkcs.12103
BULLETIN OF THE
H. Kim et al.
KOREAN CHEMICAL SOCIETY
Lithium Bromide/HBpin: A Mild and Effective Catalytic System for
the Selective Hydroboration of Aldehydes and Ketones
Hanbi Kim, Hye Lim Shin, Jaeeun Yi, Hyeon Seong Choi, Ji Hye Lee, Hyonseok Hwang, and
*
Duk Keun An
Department of Chemistry, Kangwon National University, and Institute for Molecular Science and Fusion
Technology, Chunchon, 24341, Republic of Korea. *E-mail: dkan@kangwon.ac.kr
Received July 22, 2020, Accepted September 7, 2020
The catalytic hydroboration of aldehydes and ketones with HBpin was examined using simple and com-
mercially available metal salts (Li, Na, and K). Among the tested salts, LiBr (0.5–1.0 mol%) was found to
be an efficient catalyst for the hydroboration of various aldehydes and ketones at room temperature. Fur-
ther, the chemoselective hydroboration of aldehydes over ketones was also demonstrated.
Keywords: Catalyzed hydroboration, Lithium bromide, Chemoselective reduction, Pinacolborane
(
HBpin)
Introduction
hydroboration of carbonyls and unsaturated hydrocarbons
using readily available reagents as catalysts. Furthermore,
7
Reduction reactions are fundamental and commonly used
chemical transformations in organic chemistry. For exam-
ple, the preparation of alcohols via the reduction of alde-
hydes and ketones is a well-known reaction. Among the
various methods available for this transformation, hydride
reduction reactions are often favored in terms of their yields
the hydroboration of aldehydes and ketones has also been
reported using a catalyst-free protocol under thermal condi-
8,9
8
tions. More specifically, Stachowiak et al. described the
hydroboration of aldehydes under catalyst-free conditions;
however, their method was applicable only to aldehydes,
and required high temperatures to achieve optimal conver-
sions. Moreover, the Leung group reported the catalyst-free
and solvent-free hydroboration of ketones at an elevated
1
and selectivities. In addition, the hydroboration of car-
bonyls/unsaturated hydrocarbons using a less active reduc-
tant is an important tool for the preparation of alkoxy/
boronate esters as building blocks for functionalized alco-
hols and borylation reactions, in addition to coupling agents
9
temperature.
Thus, we herein present our study into the efficient and
selective hydroboration of aldehydes and ketones with
pinacolborane using LiBr as a catalyst at room temperature.
A literature study revealed the use of LiBr as a reagent
and catalyst for the disproportionation and reduction of
aldehydes, the formation of N-acetyl enamines and N-
tosylimines, the selective cleavage of N,N-diprotected
amines, and as an additive in dearomatizing cyclization
2
in cross-coupling reactions.
Recently, numerous catalytic systems have been reported
for the hydroboration of carbonyl groups and unsaturated
hydrocarbons, with examples including transition metals,
3
main group metals, lanthanides, and nonmetal complexes.
However, in addition to being sensitive to the conditions
employed, these complexes often involve the use of toxic
reagents. Furthermore, they are expensive and require the
prepreparation of ligands. To overcome these issues,
research into alternative catalytic approaches is ongoing,
whereby the shift from complexes to commercial bench-top
reagents has received attention from an environmental and
economic standpoint.
10
reactions. We therefore employ LiBr as a promoter for
the hydroboration of aldehydes and ketones under mild
reaction conditions (Scheme 1).
Results and Discussion
Based on the above points, Zhu’s group recently reported
protocols for the catalytic hydroboration of aldehydes,
ketones, imines, and alkynes with n-BuLi. In addition, Wu
Initially, the influence of different alkali metal (Li, Na, K)-
halides (F, Cl, Br, I) was examined to develop the catalytic
system (Table 1). Thus, 1.0 mol% of the tested catalyst was
treated with HBpin (2.0 eq), followed by reaction with
4-methoxybenzaldehyde. Among the catalysts examined,
the hydroboration of 4-methoxybenzaldehyde using LiBr
and LiI as catalysts afforded 99% conversion to the desired
product after 1 h (entries 3–4, Table 1).
4
and co-workers demonstrated a general method for the cata-
lytic hydroboration of aldehydes, ketones, alkynes, and
5
alkenes with HBpin using powdered NaOH as a catalyst.
Recently, Hreczycho et al., reported the potassium-fluoride
6
mediated hydroboration of aldehydes and ketones. More
recently, our group demonstrated protocols for the catalytic
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Scheme 1. Reported catalytic hydroboration reactions and the present LiBr-mediated hydroboration system.
Under the present protocol, LiBr was selected as the cat-
alyst due to its lower cost compared to LiI. The optimized
parameters developed using LiBr are presented in Table 2.
Subsequently, the catalyst loading, solvent, stoichiome-
try, and reaction time were examined. As shown in
Table 2, the reaction of 4-methoxybenzaldehyde with
reactions in quantitative yields (Table 3, 2j and 2k). Fur-
thermore, a conjugated aldehyde (trans-cinnamaldehyde)
and ferrocene-carboxaldehyde afforded the corresponding
products in excellent yields (Table 3, 2l and 2m), and ali-
phatic aldehydes were also converted to the corresponding
alcohols (Table 3, 2n and 2o).
1
1
1
.0 mol% LiBr and HBpin (2.0 eq) in THF (1 mL) over
h afforded the boronate ester in 99% yield (entry
, Table 2). Interestingly, the reaction conversion was
The catalytic hydroboration reaction was then carried out
using ketone substrates with 1 mol% LiBr. As a result, the
corresponding boronate esters and alcohols (following
hydrolysis) were obtained in excellent yields (Table 4).
Examination of the ketone substrate scope showed that
aromatic/hetero-aromatic, conjugated, aliphatic, and bulky
ketones could be employed. Interestingly, irrespective of
the electronic and steric factors of the substituents, all
tested ketones underwent the hydroboration reaction with
excellent conversions under ambient conditions. This is
noteworthy when considering the harsh conditions
employed by recently reported thermal systems.
Following the successful reductions of both aldehydes
and ketones, the catalytic hydroboration reaction using LiBr
was applied to other organic functional groups, including
acyl chlorides, amides, nitriles, alkenes, alkynes, alkyl
halides, and epoxy groups (5 mol% LiBr, 4 eq HBpin,
THF, Table 5). It was found that only aliphatic and aro-
matic aldehydes and ketones underwent hydroboration,
thereby indicating the chemoselective nature of the present
system.
To determine the utility of the LiBr catalytic system for
chemoselective reductions, we carried out the
chemoselective hydroboration of a mixture of aldehydes
and ketones using 0.5 mol% LiBr and 1.5 eq HBPin in
THF over 1 h. Indeed, an excellent selectivity with 89%
conversion was found for benzaldehyde in the presence of
acetophenone (entry 1, Table 6). Similar results were
obtained for electron-donating (methoxy) and electron-
withdrawing (nitro) substituents (entries 2–3, Table 6). It
maintained upon decreasing the catalyst loading (1 to
.5 mol%, entry 4, Table 2). However, under more dilute
0
conditions (5 mL THF), 4% of unreacted aldehyde
remained (entry 5, Table 2). In terms of the solvent system,
neat conditions, toluene, diethyl ether, and methylene chlo-
ride gave moderate conversions along with 6–21% of the
unreacted starting material (entry 3, entries 6–8, Table 2).
In THF, 10% of the starting aldehyde remained in addition
to the desired boronate when 1.5 eq HBpin and 0.5 mol%
catalyst were employed over 6 h (entry 11, Table 2). Con-
sequently, the optimal reaction parameters were as follows:
LiBr (0.5 mol%), aldehyde (1.0 eq), and HBpin (2.0 eq), at
room temperature for 1 h (entry 4, Table 2).
With the optimal conditions in hand, the scope of the cat-
alytic hydroboration was explored using various aldehydes
and ketones. Both aliphatic and aromatic/heteroaromatic
aldehydes underwent hydroboration within an hour, giving
excellent conversions to the desired boronates. This was
followed by hydrolysis to the corresponding alcohols
(Table 3). It was found that aldehydes bearing electron
donating and electron withdrawing substituents were toler-
ated and afforded good conversions (Table 3, 2a–2i).
Importantly, alcohols 2f–2h were obtained from their
corresponding boronates in quantitative yields despite the
effects of steric hindrance from the substituents (Table 3,
2
f–2h). Moreover, hetero- and polyaromatic aldehydes also
smoothly underwent the corresponding hydroboration
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Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
Table 1. Catalyst evaluation for the hydroboration of
Table 2. Optimization of the reaction conditions.
4
-methoxybenzaldehyde.
a
Conversions were determined by the area ratio of GC.
b
Yields were determined by GC using naphthalene as an internal
standard.
a
Conversions were determined by the area ratio of GC.
b
Yields were determined by GC using naphthalene as an internal
standard.
produce the boronate ester through a ligand exchange reac-
tion. Based on the energy profile presented in Scheme 3, a
plausible mechanism is summarized in Scheme 4.
was also found that aliphatic aldehydes selectively under-
went the hydroboration reaction in the presence of aro-
matic/aliphatic ketones, with a good chemoselectivity and
yield being obtained in both cases (entries 5–6, Table 6). A
high chemoselectivity was also obtained for molecules con-
taining more than one reducible functional group (Table 6
and Scheme 2).
Subsequently, density functional theory (DFT) calcula-
tions were performed to determine the possible reaction
pathway for the LiBr-catalyzed hydroboration of aldehydes.
The energy profile for the reaction was presented in
Scheme 3. Based on this computed reaction energy profile,
the reaction pathway for the LiBr-catalyzed hydroboration
of acetaldehyde was investigated using DFT calculations at
the M06-2X/6–31 + G(d,p) level of theory. In this mecha-
nism, HBpin initially reacts with the LiBr catalyst to form
the intermediate complex INT1. The binding of aldehyde
to INT1 results in the formation of INT2 which in turn
In summary, we successfully identified an economic and
convenient method for the selective hydroboration of alde-
hydes and ketones at room temperature. Among the tested
metal halides, LiBr was found to be superior in terms of
the conversions and yields. In addition, a variety of alde-
hydes and ketones containing a wide range of substituents
were tolerated, and the hydroboration proceeded efficiently
in the presence of LiBr. Furthermore, we demonstrated that
the present system enables the chemoselective catalytic
hydroboration of aldehydes over ketones. Overall, the mild-
ness of the catalyst and the greater selectivity with almost
quantitative conversions rendered this protocol useful in the
synthesis of alcohols via catalytic hydroboration.
Experimental
General. Prior to use, all glassware was dried thoroughly
in an oven, assembled hot, and cooled under a stream of
dry nitrogen. All reactions and manipulations of air- and
moisture-sensitive materials were carried out using standard
techniques for the handling of such materials. All chemicals
were commercial products of the highest purity which were
further purified before use using standard methods. HBpin,
aldehydes, ketones, alkenes were purchased from Aldrich
undergoes
a unimolecular transformation into INT3
through a hexagonal ring transition state TS1. Then INT3
goes through another unimolecular transformation to give
INT4 via a four-membered ring transition state TS2.
Finally, the catalytic cycle is fulfilled when INT4 reacts
with a second molecule of HBpin to regenerate INT1 and
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Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
a
Table 3. Catalytic hydroboration reactions of aldehydes using
LiBr.
Table 4. Catalytic hydroboration reactions of ketones with LiBr .
a
a
Isolated yields after silica column chromatography.
a
Isolated yields after silica column chromatography.
b
LiBr used 5.0 mol% without solvent.
c
Yields were determined by NMR.
Chemical Company, Alfa Aesar, and Tokyo Chemical
1
Industry Company (TCI, Tokyo, Japan). H NMR spectra
were measured at 400 MHz with CDCl as a solvent at
3
ambient temperature unless otherwise indicated, and the
chemical shifts were recorded in parts per million down-
field from tetramethylsilane (δ = 0 ppm) or based on resid-
room temperature and stirred for 1 h. The reaction was ter-
minated by the addition of water (0.1 mL). The conversion
of the boronate ester was confirmed by GC and the crude
mixture was hydrolyzed to the alcohol by the addition of a
1 N aqueous NaOH solution (3 mL). After stirring for
13
ual CDCl (δ = 7.26 ppm) as the internal standard.
C
3
NMR spectra were recorded at 100 MHz with CDCl as a
3
solvent and referenced to the central line of the solvent
3
0 min, diethyl ether (5 mL) and NaCl were added until the
(
δ = 77.0 ppm). The coupling constants (J) are reported in
solution became supersaturated. The crude mixture was
extracted with ethyl acetate and the combined organic
hertz. Analytical thin-layer chromatography (TLC) was per-
formed on glass precoated with silica gel (Merck, silica gel
layers were dried over anhydrous MgSO . After filtration,
4
6
7
0 F254). Column chromatography was carried out using
0–230 mesh silica gel (Merck) at normal pressure. GC
the solvents were evaporated under reduced pressure and
the mixed residue was purified by silica gel column
chromatography.
analyses were performed on a Younglin Acme 6100M and
500 GC FID chromatography system, using an HP-5 cap-
6
General Procedure for the Hydroboration of Ketones
illary column (30 m). All GC yields were determined with
the use of naphthalene as the internal standard and the
authentic sample.
(
3a–k). A dry and argon-flushed flask, equipped with a
magnetic stirring bar was charged with lithium bromide
0.0009 g, 1.0 mol%), acetophenone (0.12 mL, 1.0 mmol),
(
General Procedure for the Hydroboration of Aldehydes
and THF (1 mL) at room temperature. To this,
pinacolborane (0.29 mL, 2.0 mmol) was added dropwise at
room temperature and stirred for 1 h. The reaction was ter-
minated by the addition of water (0.1 mL). The conversion
of the boronate ester was confirmed by H NMR and the
crude mixture was hydrolyzed to the alcohol by the
(
2a–o). A dry and argon-flushed flask, equipped with a
magnetic stirring bar was charged with lithium bromide
0.0004 g, 0.5 mol%), benzaldehyde (0.1 mL, 1.0 mmol),
(
1
and THF (1 mL) at room temperature. To this,
pinacolborane (0.29 mL, 2.0 mmol) was added dropwise at
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Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
Table 5. Reactivity screening of representative organic functional
groups.
addition of a 1 N aqueous NaOH solution (3 mL). After
stirring for 30 min, NaCl was added until the solution
became supersaturated. The crude mixture was extracted
with ethyl acetate and the combined organic layers were
a
dried over anhydrous MgSO . After filtration, the solvents
4
were evaporated under reduced pressure and mixed residue
was purified by silica gel column chromatography.
General Procedure for the Chemoselective Hydro-
boration of Aldehydes in the Presence of Ketones.
A
dry and argon-flushed flask, equipped with a magnetic stir-
ring bar was charged with lithium bromide (0.0004 g,
0
.5 mol%), benzaldehyde (0.10 mL, 1.0 mmol),
acetophenone (0.12 mL, 1.0 mmol), and THF (1 mL) at
room temperature (Table 6). To this, pinacolborane
(0.22 mL, 1.5 mmol) was added at room temperature and
stirred for 1 h. The reaction was terminated by the addition
of water (0.1 mL). The crude mixture was hydrolyzed to
the alcohol by the addition of a 1 N aqueous NaOH solu-
tion (3 mL). After stirring for 30 min, diethyl ether (5 mL)
and NaCl were added until solution became supersaturated.
The organic layer was extracted with ethyl acetate, the
combined organic layers were dried over anhydrous
MgSO , and the yields were calculated using GC.
4
4
,4,5,5-Tetramethyl-2-(benzyloxy)-1,3,2-dioxaborolane (1a).
1
Colorless oil; H NMR (400 MHz, CDCl ) δ 7.37–7.30 (m,
4
3
13
H), 7.27–7.24 (m, 1H), 4.92 (s, 2H), 1.25 (s, 12H);
C
NMR (100 MHz, CDCl ) δ 139.30, 128.39, 127.46,
3
1
26.81, 83.08, 66.75, 24.71. NMR data were in accordance
11
with reported literature.
4
,4,5,5-Tetramethyl-2-((4-methylbenzyl)oxy)-1,3,2-
1
dioxaborolane (1b). Colorless oil; H NMR (400 MHz,
CDCl ) δ 7.23 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz,
3
13
2
H), 4.87 (s, 2H), 2.32 (s, 3H), 1.25 (s, 12H); C NMR
(
100 MHz, CDCl ) δ 137.12, 136.32, 129.06, 126.94,
3
8
3.01, 66.67, 24.71, 21.25. NMR data were in accordance
11
with reported literature.
2
-((4-Methoxybenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-
1
dioxaborolane (1c). Colorless oil; H NMR (400 MHz,
CDCl ) δ 7.27 (d, J = 8.4 Hz, 2H), 6.85 (d, J = 8.6 Hz,
3
13
2
H), 4.84 (s, 2H), 3.79 (s, 3H), 1.25 (s, 12H); C NMR
(
100 MHz, CDCl ) δ 159.10, 131.55, 128.62, 113.75,
3
8
3.00, 66.52, 55.37, 24.63. NMR data were in accordance
11
with reported literature.
2
-((4-Fluorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-
1
dioxaborolane (1d). Colorless oil; H NMR (400 MHz,
CDCl ) δ 7.30 (dd, J = 8.3, 5.5 Hz, 2H), 7.00 (t,
3
13
J = 8.7 Hz, 2H), 4.86 (s, 2H), 1.25 (s, 12H); C NMR
100 MHz, CDCl ) δ 162.29 (d, J = 246.4 Hz), 135.05 (d,
(
3
J = 3.0 Hz), 128.72 (d, J = 8.1 Hz), 115.21(d,
J = 22.2 Hz), 83.15, 66.15, 24.70. NMR data were in
11
accordance with reported literature.
2
-((4-Chlorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-
1
dioxaborolane (1e). Colorless oil; H NMR (400 MHz,
a
CDCl ) δ 7.32–7.25 (m, 4H), 4.87 (s, 2H), 1.25 (s, 12H);
C NMR (100 MHz, CDCl ) δ 137.69, 133.10, 128.44,
3
3
Yields were determined by GC.
13
b
Yields were determined by NMR.

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Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
Table 6. Chemoselective catalytic hydroboration of aldehydes over
ketones.
129.80, 125.23, 122.54, 83.27, 65.92, 24.70. NMR data
13
were in accordance with reported literature.
-((4-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-
2
1
dioxaborolane (1h). Colorless oil; H NMR (400 MHz,
CDCl ) δ 7.44 (dd, J = 8.4, 1.8 Hz, 2H), 7.23–7.18 (m,
3
13
2
H), 4.86 (s, 2H), 1.25 (s, 12H); C NMR (100 MHz,
CDCl ) δ 138.30, 131.48, 128.50, 121.30, 83.22, 66.06,
3
2
4.70. NMR data were in accordance with reported
12
literature.
4
,4,5,5-Tetramethyl-2-((4-nitrobenzyl)oxy)-1,3,2-
1
dioxaborolane (1i). Yellow solid; H NMR (400 MHz,
CDCl ) δ 8.17 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.3 Hz,
3
13
2
H), 5.00 (s, 2H), 1.24 (s, 12H); C NMR (100 MHz,
CDCl ) δ 147.30, 146.70, 126.93, 123.68, 83.48, 65.62,
3
2
4.68. NMR data were in accordance with reported
12
literature.
2
-(Furan-2-ylmethoxy)-4,4,5,5-tetramethyl-1,3,2-
1
dioxaborolane (1j). Yellow oil; H NMR (400 MHz,
CDCl ) δ 7.36 (dd, J = 1.7, 0.9 Hz, 1H), 6.31–6.27 (m,
3
13
2
H), 4.81 (s, 2H), 1.24 (s, 12H); C NMR (100 MHz,
CDCl ) δ 152.53, 142.56, 110.34, 108.41, 83.17, 59.28,
3
2
4.68. NMR data were in accordance with reported
8
literature.
,4,5,5-Tetramethyl-2-(naphthalen-2-ylmethoxy)-1,3,2-
4
1
dioxaborolane (1k). Colorless oil; H NMR (400 MHz,
CDCl ) δ 7.87–7.76 (m, 4H), 7.50–7.40 (m, 3H), 5.10 (s,
3
13
2
H), 1.26 (s, 12H); C NMR (100 MHz, CDCl ) δ 136.79,
3
1
1
33.42, 132.92, 128.09, 128.02, 127.77, 126.13, 125.83,
25.24, 124.96, 83.17, 66.84, 24.74. NMR data were in
11
accordance with reported literature.
2
-(Cinnamyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
1
(1l). Colorless oil; H NMR (400 MHz, CDCl ) δ 7.36 (d,
3
a
Yields were determined by GC using naphthalene as an internal
J = 7.1 Hz, 2H), 7.30 (t, J = 7.5 Hz, 2H), 7.27–7.16 (m,
2H), 6.61 (d, J = 15.9 Hz, 1H), 6.27 (dt, J = 15.9, 5.3 Hz,
standard.
b
Yields were determined by NMR using 1,3,5-trimethoxybenzena as
13
1
H), 4.53 (dd, J = 5.3, 1.6 Hz, 2H), 1.26 (s, 12H);
C
an internal standard.
c
NMR (100 MHz, CDCl ) δ 136.96, 130.68, 128.62,
Using HBpin (2.0 eq).
3
d
1
27.60, 126.88, 126.54, 83.04, 65.36, 24.71. NMR data
Using HBpin (1.1 eq).
11
were in accordance with reported literature.
2
-(Ferrocenylmethoxy)pinacolborane (1m).
Yellow
1
1
28.10, 83.11, 65.95, 24.61. NMR data were in accordance
solid; H NMR (400 MHz, CDCl
J = 1.8 Hz, 2H), 4.20–4.07 (m, 7H), 1.25 (s, 12H);
) δ 4.63 (s, 2H), 4.23 (t,
3
1
2
13
with reported literature.
C
NMR (100 MHz, CDCl ) δ 85.46, 82.90, 68.52, 68.24,
3
2
1
-((2-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-
,3,2-dioxaborolane (1f). Colorless oil; H NMR
63.26, 24.75. NMR data were in accordance with reported
literature.
1
11
(
(
4
1
7
400 MHz, CDCl ) δ 7.50 (dd, J = 7.9, 1.1 Hz, 2H), 7.30
2-(Hexyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1n).
3
1
td, J = 7.6, 1.2 Hz, 1H), 7.12 (td, J = 7.7, 1.7 Hz, 1H),
Colorless oil; H NMR (400 MHz, CDCl
) δ 3.82 (t,
3
1
3
.97 (s, 2H), 1.26 (s, 12H); C NMR (100 MHz, CDCl ) δ
J = 6.6 Hz, 2H), 1.58–1.50 (m, 2H), 1.43–1.26 (m, 6H),
3
13
38.43, 132.35, 128.70, 127.88, 127.45, 121.61, 83.26,
1.24 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H); C NMR
(100 MHz, CDCl ) δ 82.68, 65.10, 31.62, 31.51, 25.37,
24.64, 22.72, 14.14. NMR data were in accordance with
7.43, 24.71. NMR data were in accordance with reported
3
8
literature.
14
reported literature.
2
1
-((3-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-
,3,2-dioxaborolane (1g). Colorless oil; H NMR
2-(Cyclohexylmethoxy)-4,4,5,5-tetramethyl-1,3,2-
dioxaborolane (1o). Colorless oil; H NMR (400 MHz,
1
1
(
1
400 MHz, CDCl ) δ 7.51 (s, 1H), 7.38 (d, J = 7.8 Hz,
CDCl ) δ 3.62 (d, J = 6.4 Hz, 2H), 1.72–1.60 (m, 5H),
3
3
13
H), 7.25–7.16 (m, 2H), 4.88 (s, 2H), 1.26 (s, 12H);
C
1.54–1.44 (m, 1H), 1.22 (s, 12H), 1.19–1.03 (m, 3H), 0.92
13
NMR (100 MHz, CDCl ) δ 141.57, 130.52, 129.97,
(td, J = 11.8, 3.1 Hz, 2H); C NMR (100 MHz, CDCl ) δ
3
3
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Lithium Bromide/HBpin
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Scheme 2. Chemoselective catalytic hydroboration of compounds containing more than one reducible group.
3
Scheme 3. Free energy profile (in kcal/mol) for the LiBr catalyzed hydroboration of aldehydes (R = CH ).
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Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
CDCl ) δ 139.33, 133.46, 128.79, 128.38, 64.68. NMR
3
15
data were in accordance with reported literature.
2-Bromophenyl)methanol (2f). White solid (181 mg,
7% yield); H NMR (400 MHz, CDCl ) δ 7.54 (dd,
(
9
1
3
J = 7.9, 1.1 Hz, 1H), 7.47 (dd, J = 7.6, 1.6 Hz, 1H), 7.33
(
4
td, J = 7.5, 1.1 Hz, 1H), 7.16 (td, J = 7.7, 1.7 Hz, 1H),
13
.74 (s, 2H), 1.98 (s, 1H); C NMR (100 MHz, CDCl ) δ
3
1
39.80, 132.71, 129.25, 129.03, 127.77, 122.70, 65.23.
15
NMR data were in accordance with reported literature.
(
9
3-Bromophenyl)methanol (2g). Colorless oil (183 mg,
1
8% yield); H NMR (400 MHz, CDCl ) δ 7.51 (s, 1H),
3
7
1
.38 (d, J = 7.3 Hz, 1H), 7.25–7.16 (m, 2H), 4.88 (s, 2H),
13
.26 (s, 12H); C NMR (100 MHz, CDCl ) δ 143.18,
3
1
30.76, 130.23, 129.99, 125.43, 122.75, 64.60. NMR data
15
were in accordance with reported literature.
(
9
4-Bromophenyl)methanol (2h). White solid (178 mg,
1
5% yield); H NMR (400 MHz, CDCl ) δ 7.52–7.43
3
(
1
m, 2H), 7.23 (d, J = 8.5 Hz, 2H), 4.66 (s, 2H), 1.67 (s,
13
H); C NMR (100 MHz, CDCl ) δ 139.84, 131.74,
3
1
28.70, 121.56, 64.71. NMR data were in accordance with
15
reported literature.
(
9
4-Nitrophenyl)methanol (2i). Pale yellow solid (147 mg,
1
6% yield);
H NMR (400 MHz, CDCl3) δ 8.21
(
1
1
d, J = 8.7 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 4.83 (s, 2H),
Scheme 4. Plausible reaction mechanism for the lithium bromide-
catalyzed hydroboration of aldehydes.
13
.90 (s, 1H); C NMR (100 MHz, CDCl ) δ 148.19,
3
47.41, 127.10, 123.86, 64.14. NMR data were in accor-
16
dance with reported literature.
Furan-2-ylmethanol (2j). Pale yellow oil (95 mg, 97%
yield); H NMR (400 MHz, CDCl ) δ 7.41–7.38 (m, 1H),
6
(100 MHz, CDCl ) δ 154.04, 142.73, 110.47, 107.91,
7
with reported literature.
Naphthalen-2-ylmethanol (2k). White solid (157 mg,
8
2.67, 70.46, 39.38, 29.40, 26.62, 25.86, 24.65. NMR data
1
1
1
were in accordance with reported literature.
3
13
Phenylmethanol (2a). Colorless oil (103 mg, 95% yield);
.36–6.27 (m, 2H), 4.61 (s, 2H), 1.42 (s, 1H); C NMR
1
H NMR (400 MHz, CDCl ) δ 7.36 (d, J = 4.4 Hz, 4H),
.33–7.26 (m, 1H), 4.69 (s, 2H), 1.98 (s, 1H); C NMR
3
3
1
3
7
7.43, 77.12, 76.80, 57.62. NMR data were in accordance
15
(
6
100 MHz, CDCl ) δ140.94, 128.69, 127.79, 127.11,
3
5.50. NMR data were in accordance with reported
15
1
literature.
9
9% yield); H NMR (400 MHz, CDCl ) δ 7.88–7.78
3
13
p-Tolylmethanol (2b). White solid (117 mg, 96% yield);
(m, 4H), 7.53–7.44 (m, 3H), 4.86 (s, 2H), 1.73 (s, 1H);
NMR (100 MHz, CDCl ) δ 138.38, 133.46, 133.03,
C
1
H NMR (400 MHz, CDCl ) δ 7.25 (d, J = 8.0 Hz, 2H),
3
3
7
.17 (d, J = 7.8 Hz, 2H), 4.64 (s, 2H), 2.34 (s, 3H), 1.57
128.47, 127.99, 127.82, 126.31, 126.03, 125.55, 125.27,
65.63. NMR data were in accordance with reported
literature.
13
(s, 1H); C NMR (100 MHz, CDCl ) δ 137.99, 137.55,
3
15
129.37, 127.24, 65.41, 21.26. NMR data were in accor-
1
6
dance with reported literature.
(E)-3-Phenylprop-2-en-1-ol (2l). White solid (130 mg,
1
(4-Methoxyphenyl)methanol (2c). White solid (133 mg,
97% yield); H NMR (400 MHz, CDCl ) δ 7.38 (dt,
3
1
96% yield);
H
NMR (400 MHz, CDCl3)
δ
7.29
J = 8.0, 1.8 Hz, 2H), 7.31 (td, J = 6.7, 6.1, 1.7 Hz, 2H),
7.26–7.21 (m, 1H), 6.61 (d, J = 15.9 Hz, 1H), 6.36 (dt,
J = 15.9, 5.7 Hz, 1H), 4.32 (d, J = 7.1 Hz, 2H), 1.48
(d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 4.61 (s, 2H),
1
3
3.80 (s, 3H), 1.59 (s, 1H); C NMR (100 MHz, CDCl3)
13
δ 159.32, 133.19, 128.78, 114.05, 65.18, 55.40. NMR data
were in accordance with reported literature.
(s, 1H); C NMR (100 MHz, CDCl ) δ 136.75, 131.27,
3
1
5
128.70, 128.57, 127.82, 126.57, 63.87. NMR data were in
17
(4-Fluorophenyl)methanol (2d). White solid (119 mg,
accordance with reported literature.
1
94% yield); H NMR (400 MHz, CDCl ) δ 7.38–7.28
Ferrocenemethanol (2m). Yellow solid (214 mg, 99%
3
13
(m, 1H), 7.08–6.99 (m, 1H), 4.66 (d, J = 4.5 Hz, 1H);
C
yield);
1
NMR (100 MHz, CDCl ) δ 163.64, 161.20, 136.67,
H NMR (400 MHz, CDCl ) δ 4.31 (d, J = 4.4 Hz, 2H),
3
3
13
136.64, 128.91, 128.83, 115.61, 115.40, 64.79. NMR data
4.25 (s, 2H), 4.22–4.11 (m, 7H), 1.49 (s, 1H); C NMR
1
5
were in accordance with reported literature.
(100 MHz, CDCl ) δ 88.71, 68.48, 68.04, 60.85. NMR data
3
17
(4-Chlorophenyl)methanol (2e). White solid (140 mg,
were in accordance with reported literature.
1
1
98% yield); H NMR (400 MHz, CDCl ) δ 7.38–7.25
Hexan-1-ol (2n). Colorless oil (95 mg, 93% yield); H
3
1
3
(m, 4H), 4.66 (s, 2H), 1.71 (s, 1H); C NMR (100 MHz,
NMR (400 MHz, CDCl ) δ 3.63 (t, J = 6.6 Hz, 2H),
3
Bull. Korean Chem. Soc. 2020
© 2020 Korean Chemical Society, Seoul & Wiley-VCH GmbH
www.bkcs.wiley-vch.de
8

BULLETIN OF THE
Article
Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
1
.60–1.51 (m, 2H), 1.36–1.24 (m, 6H), 0.93–0.80 (m, 3H);
1-(Naphthalen-2-yl)ethan-1-ol (3h). White solid (169 mg,
1
3
1
C NMR (100 MHz, CDCl ) δ 63.21, 32.87, 31.72, 25.51,
98% yield); H NMR (400 MHz, CDCl ) δ 7.85–7.80
3
3
2
2.73, 14.13. NMR data were in accordance with reported
(m, 4H), 7.52–7.43 (m, 3H), 5.07 (q, J = 6.5 Hz, 1H), 1.86
(bs, 1H), 1.58 (d, J = 6.5 Hz, 3H); C NMR (100 MHz,
18
13
literature.
Cyclohexylmethanol (2o). Colorless oil (106 mg, 93%
CDCl ) δ 143.27, 133.42, 133.02, 128.43, 128.04, 127.78,
3
1
yield); H NMR (400 MHz, CDCl ) δ 3.43 (d, J = 6.4 Hz,
126.26, 125.91, 123.91, 70.66, 25.25. NMR data were in
3
20
2H), 1.77–1.71 (m, 3H), 1.69–1.62 (m, 1H), 1.53–1.42 (m,
accordance with reported literature.
1
2
H), 1.30–1.08 (m, 4H), 0.92 (qd, J = 13.6, 12.8, 3.5 Hz,
13
(E)-4-Phenylbut-3-en-2-ol (3i). White solid (138 mg, 93%
H); C NMR (100 MHz, CDCl ) δ 68.90, 40.58, 29.64,
3
1
yield); H NMR (400 MHz, CDCl ) δ 7.37 (d, J = 8.1 Hz,
3
26.67, 25.92. NMR data were in accordance with reported
15
2H), 7.31 (t, J = 7.5 Hz, 2H), 7.27–7.21 (m, 1H), 6.56
literature.
(d, J = 15.9 Hz, 1H), 6.26 (dd, J = 15.9, 6.4 Hz, 1H), 4.48
Diphenylmethanol (3a). White solid (180 mg, 97% yield);
1
(q, J = 6.4 Hz, 1H), 1.95 (bs, 1H), 1.37 (d, J = 6.4 Hz,
H NMR (400 MHz, CDCl ) δ 7.41–7.36 (m, 4H),
3
13
3
H); C NMR (100 MHz, CDCl ) δ 136.80, 133.69,
3
7.35–7.30 (m, 4H), 7.28–7.25 (m, 2H), 5.85 (s, 1H), 2.19
13
129.47, 128.71, 127.75, 126.58, 69.02, 23.52. NMR data
(s, 1H); C NMR (100 MHz, CDCl ) δ 143.89, 128.62,
3
21
were in accordance with reported literature.
127.70, 126.64, 76.37. NMR data were in accordance with
11
reported literature.
di-p-Tolylmethanol (3b). White solid (159 mg, 75%
yield); H NMR (400 MHz, CDCl ) δ 7.27–7.25 (m, 2H),
1
Heptan-2-ol (3j). Colorless oil (96% yield); H NMR
(
400 MHz, CDCl ) δ 3.84–3.72 (m, 1H), 1.91 (bs, 1H),
3
1
3
1
.44–1.37 (m, 2H), 1.32–1.25 (m, 6H), 1.19–1.15 (m, 3H),
7.24–7.23 (m, 2H), 7.13 (d, J = 7.9 Hz, 4H), 5.79 (s, 1H),
0
.88 (t, J = 6.4 Hz, 3H); NMR data were in accordance
1
3
2.31 (s, 6H), 2.09 (bs, 1H); C NMR (100 MHz, CDCl ) δ
22
3
with reported literature.
141.19, 137.27, 129.25, 126.52, 76.04, 21.20. NMR data
1
9
1
were in accordance with reported literature.
1-Cyclohexylethan-1-ol (3k). Colorless oil (95% yield); H
NMR (400 MHz, CDCl ) δ 3.58–3.49 (m, 1H), 1.93 (bs, 1H),
1.86–1.59 (m, 6H), 1.18–1.11 (m, 5H), 1.02–0.87 (m, 3H);
1-Phenylethan-1-ol (3c). Colorless oil (116 mg, 95%
3
1
yield); H NMR (400 MHz, CDCl ) δ 7.42–7.31 (m, 4H),
3
23
7.30–7.24 (m, 1H), 4.88 (q, J = 4.3 Hz, 1H), 1.95 (bs, 1H),
NMR data were in accordance with reported literature.
1
3
1.49 (d, J = 6.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ
3
1
-(4-(Hydroxymethyl)phenyl)ethan-1-one (4a).
White
solid (147 mg, 98% yield); H NMR (400 MHz, CDCl ) δ
.99–7.92 (m, 2H), 7.49–7.42 (m, 2H), 4.77 (s, 2H), 2.60
145.92, 128.61, 127.59, 125.50, 70.52, 25.26. NMR data
1
1
1
3
were in accordance with reported literature.
7
1-(p-Tolyl)ethan-1-ol (3d). Colorless oil (127 mg, 93%
13
1
(s, 3H), 1.23 (bs, 1H); C NMR (100 MHz, CDCl
) δ
3
yield); H NMR (400 MHz, CDCl ) δ 7.26 (d, J = 8.2 Hz,
3
1
97.95, 146.22, 136.46, 128.73, 126.72, 64.75, 26.78.
2
2
H), 7.16 (d, J = 7.9 Hz, 2H), 4.86 (q, J = 6.4 Hz, 1H),
.34 (s, 3H), 1.82 (bs, 1H), 1.48 (d, J = 6.5 Hz, 3H);
24
13
NMR data were in accordance with reported literature.
C
NMR (100 MHz, CDCl ) δ 142.97, 137.27, 129.27,
3
Methyl 4-(hydroxymethyl)benzoate (4b). White solid
1
1
25.46, 70.36, 25.19, 21.20. NMR data were in accordance
(
161 mg, 97% yield); H NMR (400 MHz, CDCl ) δ 8.04
3
1
1
with reported literature.
(
3
d, J = 8.3 Hz, 2H), 7.45 (d, J = 8.1 Hz, 2H), 4.79 (s, 2H),
.92 (s, 3H), 1.75 (bs, 1H); C NMR (100 MHz, CDCl ) δ
3
13
1
-(4-Methoxyphenyl)ethan-1-ol (3e).
Colorless oil
1
(
(
(
(
150 mg, 99% yield); H NMR (400 MHz, CDCl ) δ 7.28
d, J = 8.3 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 4.83
q, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.02 (bs, 1H), 1.46
3
(ppm) 167.04, 146.01, 129.95, 129.42, 126.55, 64.81, 52.23.
25
NMR data were in accordance with reported literature.
1
3
Methyl 4-(1-hydroxyethyl)benzoate (4c). White solid
d, J = 6.5 Hz, 3H); C NMR (100 MHz, CDCl ) δ
3
1
(
171 mg, 95% yield); H NMR (400 MHz, CDCl ) δ
1
59.04, 138.12, 126.78, 113.92, 70.04, 55.38, 25.12. NMR
3
1
1
8
1
.04–7.98 (m, 2H), 7.46–7.40 (m, 2H), 4.96 (q, J = 6.5 Hz,
H), 3.90 (s, 3H), 1.49 (s, 3H); C NMR (100 MHz,
data were in accordance with reported literature.
13
1
-(4-Bromophenyl)ethan-1-ol (3f). White solid (185 mg,
1
CDCl ) δ 167.03, 150.95, 129.95, 129.32, 125.37, 70.12,
92% yield); H NMR (400 MHz, CDCl ) δ 7.49–7.42
3
3
5
2.20, 25.43. NMR data were in accordance with reported
(
(
m, 2H), 7.25–7.18 (m, 2H), 4.84 (q, J = 6.5 Hz, 1H), 1.98
bs, 1H), 1.45 (d, J = 6.5 Hz, 3H); C NMR (100 MHz,
26
1
3
literature.
CDCl ) δ 144.86, 131.65, 127.26, 121.26, 69.88, 25.35.
3
11
NMR data were in accordance with reported literature.
Acknowledgments. This study was supported by the
National Research Foundation of Korea Grant funded by
the Korean Government (2017R1D1A1B03035412 for
D. K. An and 2020R1I1A1A01073381 for J. H. Lee).
1
-(4-Nitrophenyl)ethan-1-ol (3g). Colorless oil (162 mg,
1
97% yield);
H NMR (400 MHz, CDCl3) δ 8.17
(d, J = 8.8 Hz, 2H), 7.52 (d, J = 8.7 Hz, 2H), 5.00
(
3
q, J = 6.5 Hz, 1H), 2.20 (bs, 1H), 1.49 (d, J = 6.5 Hz,
13
H); C NMR (100 MHz, CDCl ) δ 153.22, 147.23,
Supporting Information. Additional supporting informa-
tion may be found online in the Supporting Information
section at the end of the article.
3
1
26.23, 123.86, 69.59, 25.60. NMR data were in accor-
1
1
dance with reported literature.
Bull. Korean Chem. Soc. 2020
© 2020 Korean Chemical Society, Seoul & Wiley-VCH GmbH
www.bkcs.wiley-vch.de
9

BULLETIN OF THE
Article
Lithium Bromide/HBpin
KOREAN CHEMICAL SOCIETY
References
5. Y. Wu, C. Shan, J. Ying, J. Su, J. Zhu, L. L. Liu, Y. Zhao,
Green Chem. 2017, 19, 4169.
6
7
. K. Kuci ꢀn ski, G. Hreczycho, Eur. J. Org. Chem. 2020, 5, 552.
. (a) W. K. Shin, H. Kim, A. K. Jaladi, D. K. An, Tetrahedron
1
. M. B. Smith, March’s Advanced Organic Chemistry: Reac-
tions, Mechanisms, and Structure, Wiley, Hoboken, 2006,
p. 1703.
. (a) L. Koren-Selfridge, H. N. Londino, J. K. Vellucci, B. J.
Simmons, C. P. Casey, T. B. Clark, Organometallics 2009,
2
018, 74, 6310. (b) S. J. Yang, A. K. Jaladi, J. H. Kim, S.
Gundeti, D. K. An, Bull. Kor. Chem. Soc. 2019, 40, 34.
c) A. K. Jaladi, H. Kim, J. H. Lee, W. K. Shin, H. Hwang,
2
(
D. K. An, New J. Chem. 2019, 43, 16524. (d) D. H. Ma,
A. K. Jaladi, J. H. Lee, T. S. Kim, W. K. Shin, H. Hwang,
D. K. An, ACS Omega 2019, 4, 15893. (e) J. H. Kim, A. K.
Jaladi, H. T. Kim, D. K. An, Bull. Korean Chem. Soc 2019,
2
5
8, 2085. (b) J. Guo, J. Chen, Z. Lu, Chem. Commun. 2015,
1, 5725. (c) N. Eedugurala, Z. Wang, U. Chaudhary, N.
Nelson, K. Kandel, T. Kobayashi, I. I. Slowing, M. Pruski,
A. D. Sadow, ACS Catal. 2015, 5, 7399. (d) M. W. Drover,
L. L. Schafer, J. A. Love, Angew. Chem. Int. Ed. 2016, 55,
4
0, 971.
8
. H. Stachowiak, J. Kaźmierczak, K. Kuci ꢀn ski, G. Hreczycho,
Green Chem. 2018, 20, 1738.
. W. Wang, M. Luo, W. Yao, M. Ma, S. A. Pullarkat, L. Xu,
P. Leung, New J. Chem. 2019, 43, 10744.
0. (a) M. M. Mojtahedi, E. Akbarzadeh, R. Sharifi, M. S. Abaee,
Org. Lett. 2007, 9, 2791. (b) C. G. Savarin, G. N. Boice,
J. A. Murry, E. Corley, L. DiMichele, D. Hughes, Org. Lett.
3
181. (e) G. Zhang, H. Zeng, J. Wu, Z. Yin, S. Zheng, J. C.
Fettinger, Angew. Chem. Int. Ed. 2016, 128, 14581. (f) S.
Bagherzadeh, N. P. Mankad, Chem. Commun. 2016, 52,
9
3
844. (g) M. M. D. Roy, M. J. Ferguson, R. McDonald, E.
1
Rivard, Chem. Eur. J. 2016, 22, 18236. (h) J. H. Docherty, J.
Peng, A. P. Dominey, S. P. Thomas, Nat. Chem. 2017, 9,
5
95. (i) E. A. Romero, R. Jazzar, G. Bertrand, J. Organomet.
2
006, 8, 3903. (c) R. Patel, V. P. Srivastava, L. D. S. Yadav,
Chem. 2017, 829, 11. (j) M. J. Sgro, D. W. Stephan, Angew.
Chem. Int. Ed. 2012, 51, 11343. (k) F. Almqvist, L.
Torstensson, A. Gudmundsson, T. Frejd, Angew. Chem. Int.
Ed. 1997, 36, 376. (l) E. E. Korshin, G. M. Leitus, M.
Bendikov, Org. Biomol. Chem. 2014, 12, 6661.
Adv. Synth. Catal. 2010, 352, 1610. (d) J. N. Hernandez,
M. A. Ramirez, V. S. Marin, J. Org. Chem. 2003, 68, 743.
(
1
e) C. N. Rao, C. Bentz, H. Reissig, Chem. Eur. J. 2015, 21,
5951. (f) R. Santosh, Synlett 2005, 7, 1197.
1
1
1
1
1
1
1. Z. Zhu, X. Wu, X. Xu, Z. Wu, M. Xue, Y. Yao, Q. Shen, X.
3
. (a) C. C. Chong, R. Kinjo, ACS Catal. 2015, 5, 3238.
Bao, J. Org. Chem. 2018, 83, 10677.
2. T. Ghatak, K. Makarov, N. Fridman, M. S. Eisen, Chem.
Commun. 2018, 54, 11001.
(
b) C. C. Chong, H. Hirao, R. Kinjo, Angew. Chem. Int. Ed.
2
2
015, 54, 190. (c) L. Fohlmeister, A. Stasch, Chem. Eur. J.
016, 22, 10235. (d) V. K. Jakhar, M. K. Barman, S.
3. A. Baishya, S. Baruah, K. Geetharani, Dalton Trans. 2018,
Nembenna, Org. Lett. 2016, 18, 4710. (e) T. J. Hadlington,
M. Hermann, G. Frenking, C. Jones, J. Am. Chem. Soc. 2014,
4
7, 9231.
4. M. K. Barman, K. Das, B. Maji, J. Org. Chem. 2019,
4, 1570.
5. M. Pandrala, A. Resendez, S. V. Malhotra, J. Catal. 2019,
78, 283.
1
36, 3028. (f) M. Asay, C. Jones, M. Driess, Chem. Rev.
8
2
011, 111, 354. (g) D. Mukherjee, A. Ellern, A. D. Sadow,
Chem. Sci. 2014, 5, 959. (h) Z. Yang, M. Zhong, X. Ma, S.
De, C. Anusha, P. Parameswaran, H. W. Roesky, Angew.
Chem. Int. Ed. 2015, 127, 10363. (i) D. Mukherjee, S.
Shirase, T. P. Spaniol, K. Mashima, J. Okuda, Chem.
Commun. 2016, 52, 13155. (j) K. Manna, P. Ji, F. X. Greene,
W. Lin, J. Am. Chem. Soc. 2016, 138, 7488. (k) Y. Sandeep,
P. Sanjukta, S. S. Sakya, Chem. Commun. 2017, 53, 4562.
3
6. L. Koren-Selfridge, H. N. Londino, J. K. Vellucci, B. J.
Simmons, C. P. Casey, T. B. Clark, Organometallics 2009,
2
8, 2085.
1
1
1
2
2
2
2
2
2
2
7. Y. Duan, X. Du, Z. Cui, Y. Zeng, Y. Liu, T. Yang, J. Wen,
X. Zhang, J. Am. Chem. Soc. 2019, 141, 20424.
8. M. B. Runge, M. T. Mwangi, N. B. Bowden, J. Organomet.
Chem. 2006, 691, 5278.
(
l) W. Y, C. Shan, Y. Sun, P. Chen, J. Ying, J. Zhu, L. Liu,
Y. Zhao, Chem. Commun. 2016, 52, 13799. (m) L. Weidner,
C. J. Barger, M. Delferro, T. L. Lohr, T. J. Marks, ACS Catal.
9. M. Padmanaban, A. T. Biju, F. Glorius, Org. Lett. 2011,
1
3, 98.
2
017, 7, 1244. (n) S. Chen, D. Yan, M. Xue, Y. Hong, Y.
0. L. Ford, F. Atefi, R. D. Singer, P. J. Scammells, Eur. J. Org.
Chem. 2011, 2011, 942.
1. J. Wu, H. Zeng, J. Cheng, S. Zheng, J. A. Golen, D. R.
Manke, G. Zhang, J. Org. Chem. 2018, 83, 9442.
2. Z. Huang, S. Wang, X. Zhu, Q. Yuan, Y. Wei, S. Zhou, X.
Mu, Inorg. Chem. 2018, 57, 15069.
3. K. Kamata, K. Yonehara, Y. Nakagawa, K. Uehara, N.
Mizuno, Nat. Chem. 2010, 2, 478.
4. J. R. Miecznikowski, R. H. Crabtree, Polyhedron 2004,
Yao, Q. Shen, Org. Lett. 2017, 19, 3382. (o) S. R. Tamang,
M. Findlater, J. Org. Chem. 2017, 82, 2857. (p) J. R.
Lawson, L. C. Wilkins, R. L. Melen, Chem. Eur. J. 2017, 23,
1
0997. (q) D. Wu, R. Wang, Y. Li, R. Ganguly, H. Hirao, R.
Kinjo, Chem 2017, 3, 134. (r) W. Wang, X. Shen, F. Zhao,
H. Jiang, W. Yao, S. A. Pullarkat, L. Xu, M. Ma, J. Org.
Chem. 2018, 83, 69. (s) H. Stachowiak, J. Kaźmierczak, K.
Kuci ꢀn ski, G. Hreczycho, Green Chem. 2018, 20, 1738.
(
t) I. P. Query, P. A. Squier, E. M. Larson, N. A. Isley, T. B.
2
3, 2857.
5. A. P. Dieskau, J. Begouin, B. Plietker, Eur. J. Org. Chem.
011, 2011, 5291.
6. R. J. Rahaim Jr.., R. E. Maleczka Jr.., Org. Lett. 2011,
3, 584.
Clark, J. Org. Chem. 2011, 76, 6452.
4
. (a) Z. Zhu, X. Wu, X. Xu, Z. Wu, M. Xue, Y. Yao, Q. Shen,
X. Bao, J. Org. Chem. 2018, 83, 10677. (b) D. Yan, X. Wu,
J. Xiao, Z. Zhu, X. Xu, X. Bao, Y. Yao, Q. Shen, M. Xue,
Org. Chem. Front. 2019, 6, 648.
2
1
Bull. Korean Chem. Soc. 2020
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www.bkcs.wiley-vch.de
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