Selenium-Directed ortho-C-H Borylation by Iridium Catalysis

Article abstract of DOI:10.1021/acs.joc.0c01559

An iridium-catalyzed selenium-directed ortho-C-H borylation of benzyl selenide derivatives was successfully developed. This is the first example where selenium is used as a directing group in C-H borylation. The reaction was carried out using the tricyclohexylphosphine ligand for an improved catalytic efficiency. Various substrates were tolerated and afforded either ortho-monoborylated products (substrates bearing ortho-or meta-substituents) or diborylated products (substrates bearing para-substituents) in good yields. This study provides an efficient synthetic method for the preparation of a variety of organoselenium compounds.

Full text of DOI:10.1021/acs.joc.0c01559

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Note
Selenium-Directed ortho C-H Borylation by Iridium Catalysis
Jia Tang, Thishana Singh, Xingzhen Li, Linpeng Liu, and Taigang Zhou
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01559 • Publication Date (Web): 19 Aug 2020
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The Journal of Organic Chemistry
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Selenium-Directed ortho C-H Borylation by Iridium Catalysis
Jia Tang,† Thishana Singh,§ Xingzhen Li,† Linpeng Liu,† and Taigang Zhou†‡*
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†College of Chemistry and Chemical Engineering, Southwest Petroleum University, Xindu Road 8 , Chengdu, Sichuan
610500, China
‡State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Road 8,
Chengdu, Sichuan 610500, China
§College of Agriculture, Engineering and Science, School of Chemistry and Physics, University of KwaZulu-Natal, Durban
4000, South Africa
Supporting Information Placeholder
ABSTRACT: An iridium-catalyzed selenium-directed ortho C-H borylation of benzyl selenide derivatives was successfully devel-
oped. This is the first example where selenium is used as a directing group in C-H borylation. The reaction is carried out using
tricyclohexylphosphine ligand for improved catalytic efficiency. Various substrates were tolerated and afforded the ortho mono-
borylated products (substrates bearing ortho-, meta-substituents) or diborylated products (substrates bearing para-substituents) in
good yields. This study provides an efficient synthetic method for the preparation of a variety of organoselenium compounds.
1), methods using different types of directing groups were de-
veloped. These methods include having an Si-directed;9 S-di-
rected;10 P-directed;11 N-containing functional group directed;12
and O-containing functional group directed,12f, 13 substrates.
Selenium (Se) is one of the many essential trace elements that
is important for human health. However, organoselenium com-
pounds have a significantly better bioavailability than inorganic
selenium. Other advantages are its strong biological activity,
low toxicity and reduced pollution when compared to inorganic
selenium.1 As a result of the low toxicity and good biological
activity, organoselenium compounds are vital in biochemical
processes.2 It also includes anticancer, antiinflammatory, anti-
oxidant, and antiviral properties.3 Hence, the development of an
expeditious, efficient method for the synthesis of orga-
noselenium compounds is crucial.
Scheme 1. Transition-Metal-Catalyzed ortho-Directed C-H
Borylation
Organoboron compounds are amongst the most important
and effective skeletons used in organic synthesis and in the
pharmaceutical industry.4 Its efficacy is due to the boryl group
in the skeleton which can be transformed into a variety of C-
aryl, C-heteroaryl, C-X, C-NR2, C-OR, C-CN, C-SR, and C-
SeR compounds.5 There are numerous methods available to ac-
cess organoboron compounds,6 but transition-metal-catalyzed
C-H borylation is one of the most efficient, atom economical
and simple methods for the synthesis of organoboron com-
pounds.7 During the past decade, transition-metal-catalyzed or-
tho C-H borylation directed by a functional group has achieved
significant progress.8 To overcome the site selectivity and sub-
strate diversity problem during ortho C-H borylation (Scheme
To the best of our knowledge, there are currently no reports
on the use of selenium as a directing group in C-H borylation.
Thus, we hypothesized the synthesis of organoselenium com-
pounds having a boryl group via Se-directed transition-metal-
catalyzed ortho C-H borylation. This could be an efficient,
novel method for the preparation of a variety of organoselenium
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compounds since the C-B bonds can be transformed into abun- of monoborylation vs diborylation also declined when the
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8
dance of various functional groups. Thus making it possible to
quickly construct a molecular library of organic selenium com-
pounds for drug screening.
amount of HBpin increased (entry 11, 60:40). Surprisingly we
observed that there was no reaction in the absence of HBpin
(entry 10) explaining why 3.4 equiv. HBpin gave better yields
of 2a (entry 3, 76%). We also evaluated B2Pin2 in the reaction.
There was a slight decrease in conversion due to the absence of
B2Pin2 (entry 12). These results indicated that HBpin acts as the
boron source and played an important role in the formation of
the active iridium catalyst species. Since the starting material is
not completely consumed in the reaction, addition of B2Pin2
may have slightly promoted the conversion of reaction. Next,
we further reduced the catalyst loading further to 2 mol%, re-
sulting in 63% of 2a (entry 13) and decreased reactivity. Several
common bidentate and monodentate ligands, including 2,2'-bi-
pyridine L1, 4,4'-di-tert-butyl-2,2'-bipyridine L2, 1,2-bis(di-
phenylphosphino)ethane L3, tricyclohexylphosphine L4, tri-
phenylphosphine L5, tris(pentafluorophenyl)phosphine L6,
were examined in order to increase the reactivity (entries 14-
20). We found that catalytic efficiency improved when using
monodentate ligand L4 that provided 2a with the best yield (en-
try 18, 78%).
Herein we report the first example of iridium-catalyzed Se-
directed ortho C-H borylation, which is an important reaction
for late-stage modification of organoselenium compounds.
Iridium catalysts are frequently used in C-H borylation. We
examined the possible reaction conditions using [IrCl(cod)]2 as
the catalyst, and benzyl(phenyl)selane 1a as the model substrate.
To our delight, we obtained the desired ortho-borylated product
2a, but with only 29% yield (Table 1, entry 1). Different sol-
vents were tested (entries 2-5), and ethyl acetate was found to
be best, giving product 2a in 76% yield with good selectivity
(entries 3, 81:19, monoborylation vs diborylation). Usually cat-
alytic amounts of pinacolborane (HBpin) is used in the boryla-
tion reaction however, in this reaction reactivity decreased
when the quantity of HBpin decreased (entries 6-9). The ratio
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Table 1. Evaluation of Reaction Conditions for Se-Directed ortho-Borylationa
yield(%)b
entry
catalyst(mol%)
solvent
HBpin (equiv.)
ligand
ratio of 2a/2a＇
2a
29
53
76
4
2a＇
1
2
5
5
5
5
5
5
5
5
5
5
5
5
2
2
2
2
2
2
2
2
tetrahydrofuran
benzene
3.4
3.4
3.4
3.4
3.4
2.8
2.1
1.4
0.7
0
0
31
18
0
100
63:37
81:19
100
3
ethyl acetate
n-hexane
4
5
diethyl ether
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
ethyl acetate
5
0
100
6
66
51
35
23
11
4
86:14
93:7
97:3
100
7
8
1
9
0
10
11
12c
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17
18
19
20
4.1
3.4
3.4
3.4
3.4
3.4
3.4
3.4
3.4
3.4
59
71
39
15
60:40
82:18
80:20
35:65
85:15
100
63
16
35
64
L1
L2
L3
L4d
L4
L5
L6
11
2
23
0
68
25
73:27
83:17
76:24
62:38
78(65)
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16(16)
19
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aReaction conditions: 1a (0.2 mmol), B2pin2 (0.1 mmol), ligand (4 mol%), solvent (1 mL), 80 °C, 24 h. bYields were determined by GC using
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n-hexadecane as the internal calibration standard. Isolated yields in parentheses. cWithout B2pin2. d8 mol% ligand was used.
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Scheme 2. Investigation of Substrate Scope of the Se-Di-
With the optimized reaction conditions established, we began
the substrate scope investigation (Scheme 2). First, substrates
rected ortho-Monoborylationa
with electron-withdrawing groups at the ortho-position were
examined, including fluoro- (1b), chloro- (1c), bromo- (1d), tri-
fluoromethyl- (1e), and 2,3-difluoro- (1g) substituents. All
these functional groups were tolerated, and afforded only the
ortho-monoborylated products in good yields (2b-2e, 2g, 66-
80%). The substrate with the electron-donating methyl- (1f)
substituent at the ortho-position had low reactivity and gave
product 2f in 23% yield. However, the yield of product 2f in-
creased to 67% when the quantity of the catalyst and HBpin
doubled. These results show that the ortho-substituent with its
steric and electronic effects did not inhibit the reaction. Sub-
strates with meta-substituents are more challenging since
monoborylated 2 and 2,6-diborylated 2' products are obtained
in the reaction. However, the ratio of monoborylation vs di-
borylation is controlled with the use of strong electron-with-
drawing or electron-donating substituents. The substrate bear-
ing the 3-fluoro-substituent (1h) resulted in the formation of or-
tho-monoborylated 2h and 2,6-diborylated 2h' in a 40% yield
for both products. For the substrate with the stronger electron-
withdrawing, chloro-substituent (1i), the ratio of monoboryla-
tion vs diborylation improved to 61:18. To our delight, for the
substrates with even stronger electron-withdrawing substituents
such as, bromo- (1j), trifluoromethyl- (1k), 4-chloro-3-trifluo-
romethyl- (1n), at the meta-position, afforded monoborylated
products in good yield (2j, 2k, and 2n, between 69-82%) and
only trace amounts or no diborylation was observed. For sub-
strates having electron-donating methyl- (1l), and methoxy-
(1m) substituents at the meta-position showed low reactivity
and afforded the monoborylated products in low yield. The
yield of the monoborylated products improved significantly by
increasing (double) the amount of catalyst and HBpin (2l, and
2m, between 67-75%) with only trace amounts or no diboryla-
tion being observed. For substrates having electron-withdraw-
ing or electron-donating substituents, including fluoro- (1o),
chloro- (1p), trifluoromethyl- (1q), and methyl- (1r) at the para
position, a mixture of monoborylated and diborylated products
was obtained in high yield (2o-2r, between 67-97%), but with
poor regioselectivity (1.3:1-1.7:1, monoborylation vs diboryla-
tion). Furthermore, substrate bearing the heteroaryl, for exam-
ple 2-thiophene-substituent (1s), was borylated at the ortho-po-
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sition with moderate yield (2s, 59%). We also carried out the
synthesis of 1e on a larger scale (10 times, 2 mmol) and formed
product 2e in 73% yield, which demonstrates the practical util-
ity of this method as a synthetic tool.
aReaction conditions: 1 (0.2 mmol), B2pin2 (0.1 mmol), HBpin (3.4
equiv.), [IrCl(cod)]2 (2 mol%), ligand (L4, 4 mol%), EtOAc (1 mL),
80 °C, 24 h. Yields refer to isolated products. b[IrCl(cod)]2 (4
mol%), ligand (L4, 8 mol%), HBpin (6.9 equiv.).
We have noted that the regioselectivity of monoborylation
and/or diborylation in this reaction was poor for a few substrates
with meta-substituents (Scheme 2, 1h) and for most substrates
with para-substituents (Scheme 2, 1o-1r). However, the di-
borylated products for these substrates were obtained using ex-
cess HBpin, with good regioselectivity (Scheme 3, 3.9:1-7.0:1,
diborylation vs monoborylation) and yields (2a, 2h-2q, 66-
86%). Interestingly, borylation of substrate 1r with excess
HBpin still generated monoborylated 2r as the major product,
and excess HBpin inhibited the formation of diborylated prod-
uct 2r'.
We also evaluated substrates having different groups on se-
lenium (Scheme 4). Under the standard reaction conditions,
when phenyl (1a) on selenium was changed to electron with-
drawing (1t, 1u) or electron-donating (1v) substituents, we ob-
served low reactivity and low yields of the monoborylated prod-
ucts (2t-2v, 21-38%). Thus, the electronic effects of the aro-
matic ring on selenium has a great influence on the reactivity.
We also tested methyl (1w) on selenium under standard reaction
conditions and the result was the formation of monoborylated
products (2w) in 37% yield.
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Scheme 3. Investigation of Substrate Scope of Se-Directed
ence of cuprous chloride catalyst, bpy(2,2'-bipyridine), diphe-
ortho-Diborylationa
nyl disulfide or diphenyl diselenide, with good yield (70-
75%) .10a, 14 These examples demonstrate the potential synthetic
usefulness of having boryl in the substrate since it can be swiftly
converted to many organoselenium compounds containing var-
ious functional groups.
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In conclusion, we have successfully developed an iridium-
catalyzed selenium-directed ortho C-H borylation of benzyl
selenide derivatives. This is the first example that makes use of
selenium as a directing group in C-H borylation. Substrates hav-
ing ortho-substituents with steric and electronic effects did not
inhibit the reaction and only monoborylated products were ob-
tained in good yields. Substrates with meta-substituents af-
forded monoborylated and diborylated products. The mono-
and di- selectivity was also controlled in the reaction. Substrates
with para-substituents gave poor selectivity of monoborylated
and diborylated products. However, we obtained high selectiv-
ity of diborylated products in good yields by increasing the
amount of HBpin. We believe that this strategy provides an ef-
ficient synthetic method for the preparation of a variety of or-
ganoselenium compounds. An investigation on the utilization
of organoselenium products and detailed mechanistic studies
are currently in progress in the group.
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aReaction conditions: 1 (0.2 mmol), B2pin2 (0.1 mmol), HBpin
(17.2 equiv.), [IrCl(cod)]2 (2 mol%), ligand (L4, 4 mol%), EtOAc
(1 mL), 80 °C, 24 h. Yields refer to isolated products.
Scheme 4. Effect of Different Group on Selenium for Se-Di-
rected ortho-Borylationa

EXPERIMENTAL SECTION
General Information. Unless otherwise specified, all reac-
tions were carried out under nitrogen atmosphere with a dry,
sealed Schlenk tube. All reactions were monitored by thin-layer
chromatography (TLC) with glass-backed silica plates. The
TLC plates were visualized under a UV lamp. Column chroma-
tography was performed on silica gel (200-300 mesh). NMR
spectra were recorded on Bruker (400 MHz or 600 MHz) spec-
trometer. 1H NMR spectra were recorded at 400 MHz or 600
MHz in NMR solvent (CDCl3). Chemical shifts (δ) are reported
in parts per million (ppm) downfield from tetramethylsilane
(TMS, 0 ppm) or from the solvent resonance (CDCl3, 7.26 ppm).
1H NMR splitting patterns are designated as singlet (s), doublet
(d), triplet (t), quartet (q), multiplets (m), and etc. Coupling con-
stants (J) were reported in Hz and referend to apparent peak
multiplications. 13C NMR spectra were recorded at 101 MHz or
151 MHz in NMR solvents (CDCl3). Chemical shifts of carbon
are referenced to the carbon resonances of solvent (CDCl3, 77.0
ppm). Due to the quadrupole relaxation, the boron substituted
carbon is usually not observed. 19F NMR spectra were recorded
at 565 MHz in NMR solvents (CDCl3). High resolution mass
spectra (HRMS) were obtained with electrospray ionization
(ESI) or electron ionization (EI) source. The heat source for the
synthesis of substrates 1a-1w is an oil bath. The heat source for
the boronization reaction and conversion reaction is a heating
mantle.
aReaction conditions:1 (0.2 mmol), B2pin2 (0.1 mmol), HBpin (3.4
equiv.), [IrCl(cod)]2 (2 mol%), ligand (L4, 4 mol%), EtOAc (1 mL),
80 °C, 24 h. Yields refer to isolated products.
Scheme 5. Transformations of Borylation Product 2a
Compounds 1a, 1t-1v were prepared according to a reported
procedure.15 Compounds 1b-1s were prepared according to a
reported procedure.16 Compound 1w was prepared according to
a reported procedure.17
(2-Fluorobenzyl)(phenyl)selane (1b). Compound 1b was
prepared from starting from diphenyl selenide (2.5 mmol, 0.78
g, 0.5 equiv.) and 2-fluorophenylacetic acid (5.0 mmol, 0.76 g,
1 equiv.) according to the procedure described in reported liter-
ature. The crude product was purified by column chromatog-
raphy on silica gel (petroleum ether (PE) ) to afford 1b as light
Next, the boryl group in 2a was halogenated with cupric bro-
mide or cupric chloride, and formed (2-bromobenzyl) (phe-
nyl)selane 3 or (2-chlorobenzyl)(phenyl)selane 4 in moderate to
good yield (49-68%) (Scheme 5). Substrate 2a can also be
transformed to phenyl(2-((phenylselanyl)methyl)phenyl)sul-
fane 5 or a phenyl(2-(phenylselanyl)benzyl)selane 6 in the pres-
1
yellow liquid (0.65 g, 50%). H NMR (600 MHz, CDCl3) δ
7.49-7.42 (m, 2H), 7.29-7.20 (m, 3H), 7.20-7.07 (m, 1H), 7.10-
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The Journal of Organic Chemistry
-62.70. HRMS (ESI-TOF) m/z: [M] Calcd for C14H11F3Se
7.03 (m, 1H), 7.02-6.92 (m, 2H), 4.09 (s, 2H). 13C {1 H} NMR
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2
3
4
5
6
7
8
(151 MHz, CDCl3) δ 160.8 (d, J = 165.6 Hz), 134.3, 131.0 (d, J
= 3.0 Hz), 129.9, 129.1, 128.8 (d, J = 5.1 Hz), 127.7, 126.3 (d,
J = 10.1 Hz), 124.0 (d, J = 3.0 Hz), 115.5 (d, J = 15.2 Hz), 24.8
(d, J = 3.0 Hz). 19F NMR (565 MHz, CDCl3) δ -117.32. HRMS
(EI-TOF) m/z: [M] Calcd for C13H11FSe 266.0010; Found
266.0013.
315.9978; Found 315.9984.
(4-Chloro-3-(trifluoromethyl)benzyl)(phenyl)selane (1n).
Compound 1n was prepared starting with diphenyl selenide (2.5
mmol, 0.78 g, 0.5 equiv.) and 4-chloro-3-(trifluoromethyl)phe-
nylacetic acid (5.0 mmol, 1.19 g, 1 equiv.) according to the pro-
cedure described in reported literature. The crude product was
purified by column chromatography on silica gel (petroleum
ether (PE) ) to afford 1n as light yellow liquid (1.08 g, 62%).1H
NMR (400 MHz, CDCl3) δ 7.43 – 7.37 (m, 2H), 7.36 – 7.31 (m,
2H), 7.31 – 7.20 (m, 4H), 4.03 (s, 2H). 13C {1 H} NMR (151
MHz, CDCl3) δ 138.4, 134.7, 133.1, 131.5, 130.5, 129.3, 128.9,
128.3, 128.2 (q, J = 30.2 Hz), 127.9 (q, J = 6.0 Hz), 122.8 (q, J
= 273.3 Hz), 31.1. 19F NMR (565 MHz, CDCl3) δ -62.71.
HRMS (EI-TOF) m/z: [M] Calcd for C14H10ClF3Se 349.9588;
Found 349.9583.
Phenyl(2-(trifluoromethyl)benzyl)selane (1e). Compound 1e
was prepared starting with diphenyl selenide (2.5 mmol, 0.78 g,
0.5 equiv.) and 2-(trifluoromethyl)phenylacetic acid (5.0 mmol,
1.02 g, 1 equiv.) according to the procedure described in re-
ported literature. The crude product was purified by column
chromatography on silica gel(petroleum ether (PE) ) to afford
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1
1e as light yellow liquid (0.92 g, 59%). H NMR (600 MHz,
CDCl3) δ 7.63-7.58 (m, 1H), 7.52-7.46 (m, 2H), 7.40-7.33 (m,
1H), 7.31-7.17 (m, 5H), 4.24 (s, 2H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 137.8, 134.5, 131.9, 131.8, 130.2, 129.2, 128.1 (q, J
= 30.2 Hz), 127.9, 127.1, 123.3 (q, J = 4.5 Hz), 124.6 (q, J =
274.8 Hz), 28.9. 19F NMR (565 MHz, CDCl3) δ -59.51. HRMS
(EI-TOF) m/z: [M] Calcd for C14H11F3Se 315.9978; Found
315.9982.
Phenyl(4-(trifluoromethyl)benzyl)selane (1q). Compound 1q
was prepared starting with diphenyl selenide (2.5 mmol, 0.78 g,
0.5 equiv.) and 4-(trifluoromethyl)phenylacetic acid (5.0 mmol,
1.02 g, 1 equiv.) according to the procedure described in re-
ported literature. The crude product was purified by column
chromatography on silica gel(petroleum ether (PE) ) to afford
1q as white solids (1.0 g, 63%). 1H NMR (600 MHz, CDCl3) δ
7.49-7.45 (m, 2H), 7.45-7.40 (m, 2H), 7.30-7.20 (m, 5H), 4.09
(s, 2H). 13C {1 H} NMR (151 MHz, CDCl3) δ 143.2, 134.2,
129.5, 129.2（2C）, 129.1 (q, J = 33.2 Hz), 125.4 (q, J = 4.5
(2,3-Difluorobenzyl)(phenyl)selane (1g). Compound 1g was
prepared starting with diphenyl selenide (2.5 mmol, 0.78 g, 0.5
equiv.) and 2-(2,3-difluorophenyl)acetic acid (5.0 mmol, 0.86 g,
1 equiv.) according to the procedure described in reported liter-
ature. The crude product was purified by column chromatog-
raphy on silica gel (petroleum ether (PE) ) to afford 1g as light
Hz), 124.3 (q, J = 271.8 Hz), 31.7. m.p.: 56-58 C. 19F NMR
(565 MHz, CDCl3) δ -62.45. HRMS (EI-TOF) m/z: [M] Calcd
for C14H11F3Se 315.9978; Found 315.9982.
o
1
yellow liquid (0.62 g, 44%). H NMR (600 MHz, CDCl3) δ
7.48-7.43 (m, 2H), 7.31-7.21 (m, 3H), 7.03-6.94 (m, 1H), 6.93-
6.87 (m, 1H), 6.82-6.77 (m, 1H), 4.07 (s, 2H). 13C {1 H} NMR
(151 MHz, CDCl3) δ 150.6 (dd, J = 247.6, 12.1 Hz), 148.7 (dd,
J = 262.7, 13.6 Hz), 134.6, 129.4, 129.2, 129.0 (d, J = 12.1 Hz),
128.0, 125.6 (t, J = 3.0 Hz), 123.8 (dd, J = 6.0, 4.5 Hz), 115.9
(d, J = 16.6 Hz), 24.3 (t, J = 3.0 Hz). 19F NMR (565 MHz,
CDCl3) δ -138.23, -142.36. HRMS (EI-TOF) m/z: [M] Calcd
for C13H10F2Se 283.9916; Found 283.9911.
General Procedure A: Synthesis of Compounds 2a-2e, 2g-
2k, 2n-2r, 2t-2w, 2i', 2r', 2v'. In a dried Schlenk tube equipped
with a stirring bar was placed [IrCl(cod)]2 (0.004 mmol, 2.7 mg,
0.02 equiv.) and tricyclohexylphosphine (0.008 mmol, 2.2 mg,
0.04 equiv.). After evacuation and refilling three times with ni-
trogen, 1.0 mL of EtOAc was added with a syringe under nitro-
gen atmosphere. The mixture was stirred at 80 oC for 20 minutes.
Then the mixture was allowed to cool for a while, and substrate
1 (0.2 mmol, 1 equiv.), B2pin2 (0.1 mmol, 25.4 mg, 0.5 equiv.)
and HBpin (100 µL, 3.4 equiv.) were added into the mixture
under nitrogen atmosphere. The solution was stirred at 80 oC for
24 h. TLC was used to monitor the reaction process. The solu-
tion was allowed to cool to room temperature, and the solvent
was removed under reduced pressure. The crude product was
purified by column chromatography on silica gel using EtOAc
and PE (PE/EA=100/1.v/v) as eluent.
General Procedure B: Synthesis of Compounds 2f, 2l, 2m,
2s. In a dried Schlenk tube equipped with a stirring bar was
placed [IrCl(cod)]2 (0.008 mmol, 5.4 mg, 0.04 equiv.) and tri-
cyclohexylphosphine (0.016 mmol, 4.4 mg, 0.08 equiv.). After
evacuation and refilling three times with nitrogen, 1.0 mL of
EtOAc was added with a syringe under nitrogen atmosphere.
The mixture was stirred at 80 oC for 20 minutes. Then the mix-
ture was allowed to cool for a while, and substrate 1 (0.2 mmol,
1 equiv.), B2pin2 (0.1 mmol, 25.4 mg, 0.5 equiv.) and HBpin
(200 µL, 6.9 equiv.) were added into the mixture under nitrogen
(3-Fluorobenzyl)(phenyl)selane (1h). Compound 1h was
prepared starting with diphenyl selenide (2.5 mmol, 0.78 g, 0.5
equiv.) and 3-fluorophenylacetic acid (5.0 mmol, 0.76 g, 1
equiv.) according to the procedure described in reported litera-
ture. The crude product was purified by column chromatog-
raphy on silica gel (petroleum ether (PE) ) to afford 1h as light
1
yellow liquid (0.63 g, 50%). H NMR (400 MHz, CDCl3) δ
7.47-7.39 (m, 2H), 7.29-7.13 (m, 4H), 6.97-6.83 (m, 3H), 4.04
(s, 2H). 13C {1 H} NMR (101 MHz, CDCl3) δ 162.8 (d, J =
246.4 Hz), 141.4 (d, J = 8.1 Hz), 134.0, 130.0, 129.9 (2C), 129.2,
127.7, 124.6 (d, J = 3.0 Hz), 115.8 (d, J = 22.2 Hz), 113.9 (d, J
= 21.2 Hz), 31.8 (d, J = 3.0 Hz). 19F NMR (565 MHz, CDCl3) δ
-113.32. HRMS (EI-TOF) m/z: [M] Calcd for C13H11FSe
266.0010; Found 266.0007.
Phenyl(3-(trifluoromethyl)benzyl)selane (1k). Compound 1k
was prepared starting with diphenyl selenide (2.5 mmol, 0.78 g,
0.5 equiv.) and 3-(trifluoromethyl)phenylacetic acid (5.0 mmol,
1.02 g, 1 equiv.) according to the procedure described in re-
ported literature. The crude product was purified by column
chromatography on silica gel(petroleum ether (PE) ) to afford
o
atmosphere. The solution was stirred at 80 C for 24 h under
1
1k as Light yellow liquid (1.01 g, 64%). H NMR (600 MHz,
nitrogen atmosphere. TLC was used to monitor the reaction pro-
cess. The solution was allowed to cool to room temperature, and
the solvent was removed under reduced pressure. The crude
product was purified by column chromatography on silica gel
using EtOAc and PE (PE/EA=100/1.v/v) as eluent.
CDCl3) δ 7.45-7.38 (m, 3H), 7.35-7.30 (m, 3H), 7.29-7.25 (m,
1H), 7.25-7.21 (m, 2H), 4.08 (s, 2H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 140.0, 134.5, 132.2, 130.7 (q, J = 32.2 Hz), 129.3,
129.2, 129.0, 128.0, 125.7 (q, J = 4.5 Hz), 124.1 (q, J = 272.3
Hz), 123.7 (q, J = 4.5 Hz), 31.8. 19F NMR (565 MHz, CDCl3) δ
General Procedure C: Synthesis of Compounds 2a', 2h',
2o'-2q'. In a dried Schlenk tube equipped with a stirring bar,
ACS Paragon Plus Environment

The Journal of Organic Chemistry
[IrCl(cod)]2 (0.004 mmol, 2.7 mg, 0.02 equiv.) and tricyclohex-
Page 6 of 10
2H), 7.33-7.27 (m, 1H), 7.20-7.10 (m, 3H), 7.08-7.03 (m, 1H),
4.62 (s, 2H), 1.21 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3)
δ 142.9, 134.8, 134.4, 134.3, 132.2, 130.8, 128.8, 127.4 (2C),
84.1, 28.7, 24.9. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BClO2SeNa 431.0459; Found 431.0462.
1
2
3
4
5
6
7
8
ylphosphine (0.008 mmol, 2.2 mg, 0.04 equiv.) was placed. Af-
ter evacuation and refilling three times with nitrogen, 1.0 mL of
EtOAc was added with a syringe under nitrogen atmosphere.
The mixture was stirred at 80 oC for 20 minutes. Then the mix-
ture was allowed to cool for a while, and substrate 1 (0.2 mmol,
1 equiv.), B2pin2 (0.1 mmol, 25.4 mg, 0.5 equiv.) and HBpin
(500 µL, 17.2 equiv.) were added into the mixture under nitro-
gen atmosphere. The solution was stirred at 80 oC for 24 h. TLC
was used to monitor the reaction process. The solution was al-
lowed to cool to room temperature, and the solvent was re-
moved under reduced pressure. The crude product was purified
by column chromatography on silica gel using EtOAc and PE
(PE/EA=100/1.v/v) as eluent.
2-(3-Bromo-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2d). Compound 2d was prepared
using General Procedure A as a light yellow oil (59 mg, 66%).
1H NMR (600 MHz, CDCl3) δ 7.74-7.68 (m, 1H), 7.60-7.54 (m,
1H), 7.50-7.45 (m, 2H), 7.28-7.18 (m, 3H), 7.08-6.98 (m, 1H),
4.73 (s, 2H), 1.27 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3)
δ 144.5, 135.7, 135.5, 134.4, 130.8, 128.8, 127.7, 127.4, 125.9,
84.2, 31.7, 24.9. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BBrO2SeNa 474.9954; Found 474.9953.
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Procedure for the Large Scale Reaction. In a dried three-
necked flask quipped with a stirring bar was placed with
[IrCl(cod)]2 (0.04 mmol, 27 mg, 0.02 equiv.) and tricyclohex-
ylphosphine (0.08 mmol, 22 mg, 0.04 equiv.). After evacuation
and refilling three times with nitrogen, 10 mL of EtOAc was
added with a syringe under nitrogen atmosphere. The mixture
4,4,5,5-Tetramethyl-2-(2-((phenylselanyl)methyl)-3-(trifluo-
romethyl)phenyl)-1,3,2-dioxaborolane (2e). Compound 2e was
prepared using General Procedure A as a light yellow oil (67
mg, 75%). 1H NMR (600 MHz, CDCl3) δ 7.97 – 7.93 (m, 1H),
7.64 – 7.60 (m, 1H), 7.43 (m, 2H), 7.32 – 7.20 (m, 4H), 4.71 (s,
2H), 1.31 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 143.6,
139.6, 133.1, 131.4, 128.9, 128.5 (q, J = 28.7 Hz), 128.2 (q, J =
6.0 Hz), 127.2, 126.1, 123.6 (q, J = 274.8 Hz), 84.3, 27.6, 24.9.
19F NMR (565 MHz, CDCl3) δ -58.85. HRMS (ESI-TOF) m/z:
[M + Na]+ Calcd for C20H22BF3O2SeNa 465.0725; Found
465.0722.
4,4,5,5-Tetramethyl-2-(3-methyl-2–((phenylselanyl)me-
thyl)phenyl)-1,3,2-dioxaborolane (2f). Compound 2f was pre-
pared using General Procedure B as a light yellow oil (52 mg,
67%). 1H NMR (600 MHz, CDCl3) δ 7.66-7.62 (m, 1H), 7.50-
7.45 (m, 2H), 7.24-7.16 (m, 4H), 7.14-7.09 (m, 1H), 4.60 (s,
2H), 2.26 (s, 3H), 1.30 (s, 12H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 143.0, 136.7, 134.3, 133.7, 133.3, 131.6, 128.9, 127.1,
126.4, 83.7, 29.1, 24.9, 19.8. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C20H25BO2SeNa 411.1005; Found 411.1003.
2-(3,4-Difluoro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-
tetramethyl-1,3,2-dioxaborolane (2g). Compound 2g was pre-
pared using General Procedure A as a light yellow oil (64 mg,
78%). 1H NMR (600 MHz, CDCl3) δ 7.54-7.49 (m, 1H), 7.47-
7.43 (m, 2H), 7.27-7.18 (m, 3H), 7.00-6.92 (m, 1H), 4.49 (s,
2H), 1.31 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 152.2
(dd, J = 252.2, 13.6 Hz), 148.7 (dd, J = 249.2, 12.1 Hz), 136.0
(d, J = 9.1 Hz), 134.51, 132.3 (dd, J = 7.6, 4.5 Hz), 130.1, 128.9,
127.7, 114.9 (d, J = 16.6 Hz), 84.1, 25.0, 23.4. 19F NMR (565
MHz, CDCl3) δ -133.96, -142.66. HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C19H21BF2O2SeNa 433.0660; Found 433.0652.
2–(4-Fluoro-2–((phenylselanyl)methyl)phenyl)-4,4,5,5-tet-
ramethyl-1,3,2-dioxaborolane (2h). Compound 2h was pre-
pared using General Procedure A as a light yellow oil (32 mg,
40%). 1H NMR (400 MHz, CDCl3) δ 7.77 (t, 1H), 7.42 (d, J =
7.9 Hz, 2H), 7.25 – 7.19 (m, 3H), 6.86 (td, J = 8.6, 2.5 Hz, 1H),
6.66 (dd, J = 10.1, 2.2 Hz, 1H), 4.40 (s, 2H), 1.33 (s, 12H). 13C
{1 H} NMR (151 MHz, CDCl3) δ 164.4 (d, J = 250.7 Hz), 149.4
(d, J = 7.6 Hz), 138.7 (d, J = 7.6 Hz), 134.3, 130.6, 129.0, 127.5,
116.4 (d, J = 19.6 Hz), 113.1 (d, J = 19.6 Hz), 83.9, 32.2, 25.0.
19F NMR (565 MHz, CDCl3) δ -109.69. HRMS (ESI-TOF) m/z:
[M + Na]+ Calcd for C19H22BFO2SeNa 415.0754; Found
415.0756.
o
was stirred at 80 C for 20 minutes. Then the mixture was al-
lowed to cool for a while, and substrate 1e (2 mmol, 632 mg, 1
equiv.), B2pin2 (0.1 mmol, 254 mg, 0.5 equiv.) and HBpin (1000
µL, 3.4 equiv.) were added into the mixture under nitrogen at-
mosphere. The solution was stirred at 80 oC for 24 h with reflux.
TLC was used to monitor the reaction process. The solution was
allowed to cool to room temperature, and the solvent was re-
moved under reduced pressure. The crude product was purified
by column chromatography on silica gel using EtOAc and PE
(PE/EA=100/1.v/v) as eluent. The yield is 73% (644 mg).
4,4,5,5-Tetramethyl-2-(2-((phenylselanyl)methyl)phenyl)-
1,3,2-dioxaborolane (2a). Compound 2a was prepared using
1
General Procedure A as white solids (49 mg, 65%). H NMR
(400 MHz, CDCl3) δ 7.88-7.73 (m, 1H), 7.47-7.42 (m, 2H),
7.29-7.12 (m, 5H), 7.08-6.94 (m, 1H), 4.47 (s, 2H), 1.34 (s,
12H). 13C {1 H} NMR (101 MHz, CDCl3) δ 146.0, 136.5, 133.9,
131.2, 130.8, 129.49, 128.9, 127.2, 126.2, 83.8, 32.6, 25.0. m.p.:
63-65 oC. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H23BO2SeNa 397.0849; Found 397.0844.
2,2'-(2-((Phenylselanyl)methyl)-1,3-phenylene)bis(4,4,5,5-
tetramethyl-1,3,2-dioxaborolane) (2a'). Compound 2a' was
prepared using General Procedure C as white solids (86 mg,
86%). 1H NMR (600 MHz, CDCl3) δ 7.76-7.71 (m, 2H), 7.32-
7.26 (m, 2H), 7.15-7.06 (m, 4H), 4.90 (s, 2H), 1.20 (s, 24H). 13
C
{1 H} NMR (151 MHz, CDCl3) δ 152.5, 138.7, 134.1, 131.6,
128.6, 126.9, 125.3, 83.7, 31.0, 24.9. m.p.: 109-110 oC. HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C25H34B2O4SeNa
523.1701; Found 523.1701.
2-(3-Fluoro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaboolane (2b). Compound 2b was prepared
using General Procedure A as a light yellow oil (62 mg, 80%).
1H NMR (600 MHz, CDCl3) δ 7.51-7.45 (m, 1H), 7.42-7.35 (m,
2H), 7.18-7.09 (m, 3H), 7.09-7.05 (m, 1H), 6.96-6.91 (m, 1H),
4.44 (s, 2H), 1.24 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3)
δ 160.8 (d, J = 247.6 Hz), 134.2, 132.8 (d, J = 12.1 Hz), 131.9
(d, J = 4.5 Hz), 130.7, 128.8, 127.7 (d, J = 7.5 Hz), 127.3, 119.0
(d, J = 22.6 Hz), 84.0, 25.0, 23.7 (d, J = 4.5 Hz). 19F NMR (565
MHz, CDCl3) δ -117.53. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C19H22BFO2SeNa 415.0754; Found 415.0755.
2-(3-Chloro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2c). Compound 2c was prepared
using General Procedure A as a light yellow oil (62 mg, 76%).
1H NMR (600 MHz, CDCl3) δ 7.70-7.47 (m, 1H), 7.42-7.37 (m,
2,2-(4-Fluoro-2-((phenylselanyl)methyl)-1,3-phnylene)bis
(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2h'). Compound
2h' was prepared using General Procedure C as white solids(86
1
mg, 83%). H NMR (600 MHz, CDCl3) δ 7.76 (t, J = 7.4 Hz,
1H), 7.43-7.37 (m, 2H), 7.22-7.15 (m, 3H), 6.88-6.80 (m, 1H),
4.81 (s, 2H), 1.33 (s, 12H), 1.26 (s, 12H). 13C {1 H} NMR (151
ACS Paragon Plus Environment

Page 7 of 10
The Journal of Organic Chemistry
2-(5-Chloro-2–((phenylselanyl)methyl)-4-(trifluoromethyl)
MHz, CDCl3) δ 168.5 (d, J = 250.7 Hz), 153.6 (d, J = 7.5 Hz),
1
2
3
4
5
6
7
8
140.2 (d, J = 10.6 Hz), 133.8, 131.3, 128.8, 127.1, 112.9 (d, J =
22.6 Hz), 84.2, 83.9, 30.9, 25.0, 24.9. m.p.: 80-82 oC. 19F NMR
(565 MHz, CDCl3) δ -99.03. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C25H33B2FO4SeNa 541.1606; Found 541.1605.
2-(4-Chloro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2i). Compound 2i was prepared
using General Procedure A as a light yellow oil (50 mg, 61%).
1H NMR (600 MHz, CDCl3) δ 7.66-7.60 (m, 1H), 7.37-7.30 (m,
2H), 7.21-7.12 (m, 3H), 7.09-7.04 (m, 1H), 6.84 (s, 1H), 4.30
(s, 2H), 1.25 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ
148.2, 137.9, 136.7, 134.4, 130.5, 129.5, 129.0, 127.6, 126.3,
84.0, 32.0, 25.0. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BClO2SeNa 431.0453; Found 431.0456.
phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2n) Com-
pound 2n was prepared using General Procedure A as a light
yellow oil (78 mg, 82%). 1H NMR (600 MHz, CDCl3) δ 7.84 (s,
1H), 7.35-7.30 (m, 2H), 7.25-7.22 (m, 1H), 7.21-7.16 (m, 2H),
6.99 (s, 1H), 4.33 (s, 2H), 1.33 (s, 12H). 13C {1 H} NMR (151
MHz, CDCl3) δ 145.3, 138.9, 135.0, 129.6, 129.5, 129.4, 129.3,
129.1, 128.1 (q, J = 4.5 Hz), 122.7 (q, J = 273.3 Hz), 84.6, 31.6,
25.0. 19F NMR (565 MHz, CDCl3) δ -63.06. HRMS (EI-TOF)
m/z: [M] Calcd for C20H21BClF3O2Se 476.0440; Found
476.0447.
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2-(5-Fluoro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2o). Compound 2o was prepared
1
using General Procedure A as white solids (36 mg, 46%). H
2,2'-(4-Chloro-2-(phenylselanyl)methyl)-1,3-phenylene)
bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2i'). Compound
2i' was prepared using General Procedure A as white solids (19
NMR (600 MHz, CDCl3) δ 7.41-7.36 (m, 1H), 7.36-7.32 (m,
2H), 7.18-7.11 (m, 3H), 6.88-6.79 (m, 2H), 4.33 (s, 2H), 1.27
(s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 161.3 (d, J =
246.1 Hz), 141.8 (d, J = 3.0 Hz), 134.1, 131.1 (d, J = 7.5 Hz),
130.7, 128.9, 127.4, 122.6 (d, J = 19.6 Hz), 117.4 (d, J = 22.6
1
mg, 18%). H NMR (600 MHz, CDCl3) δ 7.69-7.65 (m, 1H),
7.45-7.40 (m, 2H), 7.23-7.18 (m, 3H), 7.18-7.14 (m, 1H), 4.66
(s, 2H), 1.36 (s, 12H), 1.26 (s, 12H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 150.7, 141.0, 138.5, 133.1, 131.9, 128.8, 126.9, 126.5,
84.6, 83.9, 31.3, 25.0, 24.9. m.p.: 100-101 oC. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C25H33B2ClO4SeNa 557.1311; Found
557.1314.
2-(4-Bromo-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2j). Compound 2j was prepared
using General Procedure A as a light yellow oil (63 mg, 69%).
1H NMR (600 MHz, CDCl3) δ 7.66-7.62 (m, 1H), 7.43-7.39 (m,
2H), 7.33-7.29 (m, 1H), 7.28-7.21 (m, 3H), 7.06 (s, 1H), 4.36
(s, 2H), 1.33 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ
148.3, 138.0, 134.4, 132.4, 130.4, 129.2, 129.0, 127.6, 125.3,
84.0, 32.0, 25.0. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BBrO2SeNa 474.9954; Found 474.9957.
o
Hz), 84.1, 31.8, 25.0. m.p.: 65-57 C. 19F NMR (565 MHz,
CDCl3) δ -117.07. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BFO2SeNa 415.0754; Found 415.0749.
2,2-(5-Fluoro-2-((phenylselanyl)methyl)-1,3-phenylene)bis
(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2o'). Compound
2o' was prepared using General Procedure C as white solids (73
1
mg, 70%). H NMR (600 MHz, CDCl3) δ 7.50-7.46 (m, 2H),
7.37-7.33 (m, 2H), 7.23-7.14 (m, 3H), 4.91 (s, 2H), 1.27 (s,
24H). 13C {1 H} NMR (151 MHz, CDCl3) δ 160.6 (d, J = 247.6
Hz), 148.3, 134.2, 131.3, 128.7, 127.1,124.7 (d, J = 19.6 Hz),
84.0, 30.1, 24.9. m.p.: 99-101 oC. 19F NMR (565 MHz, CDCl3)
δ -118.59. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C25H33B2FO4SeNa 541.1606; Found 541.1605.
2-(5-Chloro-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tetra-
methyl-1,3,2-dioxaborolane (2p). Compound 2p was prepared
4,4,5,5-Tetramethyl-2-(2-((phenylselanyl)methyl)-4-(trifluo-
romethyl)phenyl)-1,3,2-dioxaborolane (2k). Compound 2k was
prepared using General Procedure A as a light yellow oil (70
1
using General Procedure A as white solids (34 mg, 42%). H
NMR (600 MHz, CDCl3) δ 7.67 (s, 1H), 7.36-7.31 (m, 2H),
7.21-7.06 (m, 4H), 6.82-6.78 (m, 1H), 4.31 (s, 2H), 1.27 (s,
12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 144.6, 136.1, 134.3,
134.2, 132.2, 130.8, 130.6, 129.0, 127.5, 84.2, 31.9, 25.0. m.p.:
92-94 oC. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H22BClO2SeNa 431.0459; Found 431.0455.
1
mg, 80%). H NMR (600 MHz,CDCl3) δ 7.91-7.86 (m, 1H),
7.41-7.38 (m, 1H), 7.38-7.34 (m, 2H), 7.28-7.18 (m, 3H), 7.03
(s, 1H), 4.42 (s, 2H), 1.36 (s, 12H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 147.1, 136.9, 134.8, 132.1 (q, J = 31.7 Hz), 129.9,
129.0, 127.8, 125.8 (q, J = 3.0 Hz), 124.0 (q, J = 273.3 Hz),
122.5 (q, J = 3.0 Hz), 84.3, 32.3, 25.0. 19F NMR (565 MHz,
CDCl3) δ -63.21. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C20H22BF3O2SeNa 465.0722; Found 465.0724.
4,4,5,5-Tetramethyl-2-(4-methyl-2-((phenylselanyl)methyl)
phenyl)-1,3,2-dioxaborolane (2l). Compound 2l was prepared
using General Procedure B as a light yellow oil (58 mg, 75%).
1H NMR (600 MHz, CDCl3) δ 7.74-7.65 (m, 1H), 7.49-7.41 (m,
2H), 7.26-7.16 (m, 3H), 7.01 (s, 1H), 6.83 (s, 1H), 4.45 (s, 2H),
2.24 (s, 3H), 1.34 (s, 12H). 13C {1 H}0 NMR (151 MHz, CDCl3)
δ 145.8, 140.9, 136.7, 133.9, 131.4, 130.5, 128.8, 127.1, 127.0,
83.6, 32.6, 25.0, 21.6. HRMS (ESI-TOF) m/z: [M + Na]+ Calcd
for C20H25BO2SeNa 411.1005; Found 411.1007.
2-(4-Methoxy-2-((phenylselanyl)methyl)phenyl)-4,4,5,5-tet-
ramethyl-1,3,2-dioxaborolane (2m). Compound 2m was pre-
pared using General Procedure B as a light yellow oil (54 mg,
67%). 1H NMR (600 MHz, CDCl3) δ 7.70-7.64 (m, 1H), 7.42-
7.35 (m, 2H), 7.19-7.10 (m, 3H), 6.69-6.59 (m, 1H), 6.41 (s,
1H), 4.35 (s, 2H), 3.59 (s, 3H), 1.25 (s, 12H). 13C {1 H} NMR
(151 MHz, CDCl3) δ 161.5, 148.3, 138.3, 134.1, 131.1, 128.9,
127.2, 114.8, 112.0, 83.5, 55.1, 32.7, 25.0. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C20H25BO3SeNa 427.0954; Found
427.0958.
2,2'-(5-Chloro-2-((phenylselanyl)methyl)-1,3-phenylene)
bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2p'). Compound
2p' was prepared using General Procedure C as white solids (70
1
mg, 66%). H NMR (600 MHz, CDCl3) δ 7.76 (s, 2H), 7.37-
7.32 (m, 2H), 7.22-7.14 (m, 3H), 4.89 (s, 2H), 1.27 (s, 24H). 13
C
{1 H} NMR (151 MHz, CDCl3) δ 151.1, 138.1, 134.4, 131.7,
131.0, 128.7, 127.2, 84.0, 30.2, 24.9. m.p.: 136-138 oC. HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C25H33B2ClO4SeNa
557.1311; Found 557.1310.
4,4,5,5-Tetramethyl-2-(2-((phenylselanyl)methyl)-5-(trifluo-
romethyl)phenyl)-1,3,2-dioxaborolane (2q). Compound 2q was
prepared using General Procedure A as white solids (54 mg,
61%). 1H NMR (600 MHz, CDCl3) δ 7.96 (s, 1H), 7.41-7.29 (m,
3H), 7.22-7.11 (m, 3H), 6.96-6.89 (m, 1H), 4.36 (s, 2H), 1.28
(s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 150.4, 134.4,
133.2 (q, J = 3.0 Hz), 130.3, 129.5, 129.0, 128.3 (q, J = 33.2
Hz), 127.7, 127.3 (q, J = 3.0 Hz), 124.4 (q, J = 273.3 Hz), 84.3,
o
32.1, 25.0. m.p.: 80-82 C. 19F NMR (565 MHz, CDCl3) δ -
62.37. HRMS (EI-TOF) m/z: [M] Calcd for C20H22BF3O2Se
442.0830; Found 442.0826.
2,2'-(2-((Phenylselanyl)methyl)-5-(trifluoromethyl)-1,3-phe-
nylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane
)(2q').
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Compound 2q' was prepared using General Procedure C as
(d, J = 7.8 Hz, 2H), 7.25-7.14 (m, 2H), 6.92-6.85 (m, 1H), 6.77-
white solids (80 mg, 70%). 1H NMR (600 MHz, CDCl3) δ 8.03
(s, 2H), 7.34-7.31 (m, 2H), 7.23-7.19 (m, 1H), 7.18-7.14 (m,
2H), 4.97 (s, 2H), 1.29 (s, 24H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 156.9, 135.0, (q, J = 3.0 Hz), 134.5, 130.6, 128.7,
127.4, 127.2, 124.6 (q, J = 271.8 Hz), 84.1, 30.5, 24.9. m.p.:
6.71 (m, 2H), 4.34 (s, 2H), 3.78 (s, 3H), 1.35 (s, 12H). 13C {1
H} NMR (151 MHz, CDCl3) δ 159.6, 146.5, 136.8, 136.5, 130.7,
129.5, 126.0, 120.9, 114.5, 83.8, 55.4, 33.6, 25.1. HRMS (ESI-
TOF) m/z: [M + Na]+ Calcd for C20H25BO3SeNa 427.0954;
Found 427.0956.
1
2
3
4
5
6
7
8
o
113-115 C. 19F NMR (565 MHz, CDCl3) δ -62.31. HRMS
2,2'-(2-(((4-Methoxyphenyl)selanyl)methyl)-1,3-phenylene)
bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2v'). Compound
2v' was prepared using General Procedure A as white solids (11
(ESI-TOF) m/z: [M + Na]+ Calcd for C26H33B2F3O4SeNa
591.1574; Found 591.1573.
1
4,4,5,5-Tetramethyl-2-(5-methyl-2-((phenylselanyl)me-
thyl)phenyl)-1,3,2-dioxaborolane (2r). Compound 2r was pre-
pared using General Procedure A as white solids (35 mg, 45%).
1H NMR (600 MHz, CDCl3) δ 7.53 (s, 1H), 7.40-7.35 (m, 2H),
7.14 (s, 3H), 7.01-6.97 (m, 1H), 6.89-6.84 (m, 1H), 4.37 (s, 2H),
2.23 (s, 3H), 1.26 (s, 12H). 13C {1 H} NMR (151 MHz, CDCl3)
δ 142.9, 137.1, 135.7, 133.7, 131.6, 131.5, 129.5, 128.8, 127.0,
83.8, 32.4, 25.0, 21.1. m.p.: 53-54 oC. HRMS (ESI-TOF) m/z:
[M + Na]+ Calcd for C20H25BO2SeNa 411.1005; Found
411.1004.
mg, 10%). H NMR (600 MHz, CDCl3) δ 7.83-7.78 (m, 2H),
9
7.25-7.20 (m, 2H), 7.20-7.13 (m, 1H), 6.71-6.66 (m, 2H), 4.86
(s, 2H), 3.74 (s, 3H), 1.27 (s, 24H). 13C {1 H} NMR (151 MHz,
CDCl3) δ 159.4, 153.3, 138.6, 137.0, 125.1, 121.1, 114.3, 83.6,
55.3, 31.7, 25.0. m.p.: 108-110 oC. HRMS (ESI-TOF) m/z: [M
+ Na]+ Calcd for C26H36B2O5SeNa 553.1806; Found 553.1806.
4,4,5,5-Tetramethyl-2-(2-((methylselanyl)methyl)phenyl)-
1,3,2-dioxaborolane (2w). Compound 2w was prepared using
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
General Procedure A as a light yellow oil (23 mg, 37%). H
NMR (600 MHz, CDCl3) δ 7.72 (d, J = 7.3 Hz, 1H), 7.29-7.23
(m, 1H), 7.15-7.08 (m, 2H), 4.00 (s, 2H), 1.80 (s, 3H), 1.29 (s,
12H).13C {1 H} NMR (151 MHz, CDCl3) δ 146.8, 136.5, 130.7,
129.4, 126.0, 83.8, 28.4, 25.0, 4.3. HRMS (ESI-TOF) m/z: [M
+ Na]+ Calcd for C14H21BO2SeNa 335.0692; Found 335.0692.
(2-Bromobenzyl)(phenyl)selane (3). 4,4,5,5-tetramethyl-2–
(2–((phenylselanyl)methyl)phenyl)-1,3,2-dioxaborolane (40.0
mg, 0.115 mmol, 1.0 equiv) and CuBr2 (77.1 mg, 0.345 mmol,
3.0 equiv.) were dissolved in MeOH (1.0 mL)/H2O (1.0 mL)
and stirred at 80 °C for 24 h. Then the mixture was allowed to
cool to room temperature. The mixture was extracted with
EtOAc (5 mL×3). Organic layers were combined, dried over
anhydrous MgSO4, filtered and concentrated under vacuum.
The crude product was purified by column chromatography on
silica gel using EtOAc and PE as eluent to obtain (2-bromoben-
zyl)(phenyl)selane (25 mg, 68%) as a light yellow oil.14 1H
NMR (600 MHz, CDCl3) δ 7.55-7.50 (m, 1H), 7.50-7.45 (m,
2H), 7.30-7.19 (m, 3H), 7.13-7.08 (m, 1H), 7.07-6.99 (m, 2H),
4.18 (s, 2H). 13C {1 H} NMR (151 MHz, CDCl3) δ 138.4, 134.6,
133.2, 130.7, 129.9, 129.1, 128.6, 127.8, 127.4, 124.5, 33.1 The
spectral data were in accordance with literature16.
(2-Chlorobenzyl)(phenyl)selane (4). 4,4,5,5-tetramethyl-2-
(2-((phenylselanyl)methyl)phenyl)-1,3,2-dioxaborolane (46.8
mg, 0.125 mmol, 1.0 equiv.) and CuCl2 (64 mg, 0.375 mmol,
3.0 equiv.) were dissolved in MeOH (1.0 mL)/H2O (1.0 mL)
and stirred at 80 °C for 6 h. Then the mixture was allowed to
cool to room temperature. The mixture was extracted with
EtOAc (5 mL×3). Organic layers were combined, dried over
anhydrous MgSO4, filtered and concentrated under vacuum.
The crude product was purified by column chromatography on
silica gel using EtOAc and PE as eluent to obtain (2-chloroben-
zyl)(phenyl)selane (17 mg, 49%) as a light yellow oil.18 1H
NMR (400 MHz, CDCl3) δ 7.48-7.43 (m, 2H), 7.34-7.30 (m,
1H), 7.28-7.18 (m, 3H), 7.14-6.98 (m, 3H), 4.16 (s, 2H). 13C {1
H} NMR (101 MHz, CDCl3) δ 136.7, 134.5, 133.9, 130.7, 129.9,
129.8, 129.1, 128.4, 127.7, 126.7, 30.1. The spectral data were
in accordance with literature19.
2,2'-(5-Methyl-2-((phenylselanyl)methyl)-1,3-phenylene) bis
(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (2r'). Compound 2r'
was prepared using General Procedure A as white solids (34 mg,
33%). 1H NMR (600 MHz, CDCl3) δ 7.63 (s, 2H), 7.40-7.35 (m,
2H), 7.19-7.14 (m, 3H), 4.95 (s, 2H), 2.30 (s, 3H), 1.27 (s, 24H).
13C {1 H} NMR (151 MHz, CDCl3) δ 149.4, 139.3, 134.5, 133.9,
o
132.0, 128.6, 126.8, 83.6, 30.7, 24.9, 20.9. m.p.: 172-173 C.
HRMS (EI-TOF) m/z: [M] Calcd for C26H36B2O4Se 514.1965;
Found 514.1963.
4,4,5,5-Tetramethyl-2-(2-((phenylselanyl)methyl)thiophen-
3-yl)-1,3,2-dioxaborolane (2s). Compound 2s was prepared us-
ing General Procedure B as a light yellow solids (45 mg, 59%).
1H NMR (600 MHz, CDCl3) δ 7.52-7.46 (m, 2H), 7.26-7.20 (m,
3H), 7.19-7.16 (m, 1H), 7.10-7.07 (m, 1H), 4.65 (s, 2H), 1.29
(s, 12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 154.9, 134.0,
133.0, 130.5, 129.0, 127.5, 123.7, 83.6, 25.8, 25.0. m.p.: 85-87
oC. HRMS (ESI-TOF) m/z: [M
+
Na]+ Calcd for
C17H21BO2SSeNa 403.0413; Found 403.0418.
2-(2-(((4-Fluorophenyl)selanyl)methyl)phenyl)-4,4,5,5-tet-
ramethyl-1,3,2-dioxaborolane (2t). Compound 2t was prepared
using General Procedure A as a light yellow oil (16 mg, 21%).
1H NMR (600 MHz, CDCl3) δ 7.83-7.78 (m, 1H), 7.39-7.33 (m,
2H), 7.25-7.16 (m, 2H), 6.93-6.87 (m, 3H), 4.38 (s, 2H), 1.35
(s, 12H), 13C {1 H} NMR (151 MHz, CDCl3) δ 162.7 (d, J =
247.6 Hz), 146.0, 136.8, 136.7 (d, J = 31.7 Hz), 130.7, 129.4,
126.2, 121.2 (d, J = 3.0 Hz), 115.9 (d. J = 21.1 Hz), 83.8, 33.4,
25.0. 19F NMR (565 MHz, CDCl3) δ -114.62. HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C19H22BFO2SeNa 415.0754; Found
415.0748.
4,4,5,5-Tetramethyl-2-(2-(((4–(trifluoromethyl)phenyl)se-
lanyl)methyl)phenyl)-1,3,2-dioxaborolane (2u). Compound 2u
was prepared using General Procedure A as a light yellow oil
(19 mg, 22%). 1H NMR (600 MHz, CDCl3) δ 7.84-7.80 (m, 1H),
7.55-7.51 (m, 2H), 7.47-7.43 (m, 2H), 7.33-7.27 (m, 1H), 7.22
(t, J = 7.3 Hz, 1H), 7.12-7.07 (m, 1H), 4.53 (s, 2H), 1.33 (s,
12H). 13C {1 H} NMR (151 MHz, CDCl3) δ 145.1, 136.9, 136.7,
132.8, 131.0, 129.5, 129.0 (q, J = 30.2 Hz), 126.6, 125.5 (q, J =
3.0 Hz), 124.3 (q, J = 271.8 Hz), 83.9, 32.3, 25.0. 19F NMR (565
MHz, CDCl3) δ -62.56. HRMS (ESI-TOF) m/z: [M + Na]+
Calcd for C20H22BF3O2SeNa 465.0722; Found 465.0724.
2-(2-(((4-Methoxyphenyl)selanyl)methyl)phenyl)-4,4,5,5-tet-
ramethyl-1,3,2-dioxaborolane (2v). Compound 2v was pre-
pared using General Procedure A as a light yellow oil (31 mg,
Phenyl(2-((phenylselanyl)methyl)phenyl)sulfane (5). 4,4,5,5-
tetramethyl-2-(2-((phenylselanyl)methyl)phenyl)-1,3,2-diox-
aborolane (46.8 mg, 0.125 mmol, 1.0 equiv.), diphenyl disulfide
(15.2 mg, 0.069 mmol, 0.55 equiv), CuCl (1.3 mg, 0.0125 mmol,
0.1 equiv.), 2,2'-bipyridine (1.9 mg, 0.0125 mol, 0.1 equiv.) and
DMSO (1 mL)/H2O (0.5 mL) were added into a Schlenk tube.
The mixture was stirred at 80 °C for 10 h. Then the mixture was
allowed to cool to room temperature. The mixture was extracted
1
38%). H NMR (600 MHz, CDCl3) δ 7.82-7.76 (m, 1H), 7.32
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The Journal of Organic Chemistry
ACKNOWLEDGMENT
with EtOAc (5 mL×3). Organic layers were combined, dried

1
2
3
4
5
6
7
8
over anhydrous MgSO4, filtered and concentrated under vac-
uum. The crude product was purified by column chromatog-
raphy on silica gel using EtOAc and PE as eluent to obtain (2-
bromobenzyl)(phenyl)selane (31 mg, 70%) as a light yellow
oil.18 1H NMR (600 MHz, CDCl3) δ 7.51-7.37 (m, 5H), 7.36-
7.22 (m, 6H), 7.15-7.05 (m, 3H), 4.30 (s, 2H). 13C {1 H} NMR
(151 MHz, CDCl3) δ 140.5, 136.4, 134.2, 133.8, 132.9, 130.5,
130.3 (2C), 129.3, 129.1, 128.1, 127.8, 127.6, 126.8, 31.1.
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C19H16SSeNa
379.0030; Found 379.0034.
We are grateful for the financial support from the National Natural
Science Foundation of China (Nos. 21602184 and 21811530004),
Youth Science and Technology Innovation Team of SWPU
(No.2017CXTD05).

REFERENCES
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Phenyl(2-(phenylselanyl)benzyl)selane (6).4,4,5,5-tetrame-
thyl-2-(2-((phenylselanyl)methyl)phenyl)-1,3,2-dioxaborolane
(46.8 mg, 0.125 mmol, 1.0 equiv.), diphenyl diselenide (21.5
mg, 0.064 mmol, 0.55 equiv.), CuCl (1.3 mg, 0.0125 mmol,
0.10 equiv.), 2,2'-bipyridine (1.9 mg, 0.0125 mol, 0.10 equiv.)
and DMSO (1 mL)/H2O (0.5 mL) were added into a Schlenk
tube. The mixture was stirred at 80 °C for 10 h. Then the mix-
ture was allowed to cool to room temperature. The mixture was
extracted with EtOAc (5 mL×3). Organic layers were combined,
dried over anhydrous MgSO4, filtered and concentrated under
vacuum. The crude product was purified by column chromatog-
raphy on silica gel using EtOAc and PE as eluent to obtain (2-
bromobenzyl)(phenyl)selane (37.8 mg, 75%) as a light yellow
oil.18 1H NMR (600 MHz, CDCl3) δ 7.42-7.28 (m, 5H), 7.21-
7.14 (m, 6H), 7.07-6.97 (m, 3H), 4.22 (s, 2H). 13C {1 H} NMR
(151 MHz, CDCl3) δ 140.7, 135.2, 134.3, 132.9, 132.2, 131.6,
130.4, 130.1, 129.5, 129.1, 128.1, 127.9, 127.6, 127.4, 33.4.
HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C19H16Se2H
404.9655; Found 404.9651.
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
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Compound characterization data (PDF).

AUTHOR INFORMATION
Corresponding Author
Taigang Zhou − College of Chemistry and Chemical Engineering
& State Key Laboratory of Oil and Gas Reservoir Geology and
Exploitation, Southwest Petroleum University, Xindu Road 8,
Chengdu, Sichuan 610500, China.
ocrid.org/0000-0002-3208-067X; Email: tgzhou@swpu.edu.cn
Authors
(6) (a) Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J.
M.; Hartwig, J. F., C−H Activation for the Construction of C−B
Bonds. Chem. Rev. 2010, 110, 890-931; (b) Lv, J.; Chen, X.; Xue,
X.-S.; Zhao, B.; Liang, Y.; Wang, M.; Jin, L.; Yuan, Y.; Han, Y.;
Zhao, Y.; Lu, Y.; Zhao, J.; Sun, W.-Y.; Houk, K. N.; Shi, Z., Metal-
free directed sp2-C–H borylation. Nature 2019, 575, 336-340; (c)
Li, Y.; Wu, X. F., Direct C-H Bond Borylation of (Hetero)Arenes:
Evolution from Noble Metal to Metal Free. Angew. Chem. Int. Ed.
Engl. 2020, 59, 1770-1774; (d) Candish, L.; Teders, M.; Glorius,
F., Transition-Metal-Free, Visible-Light-Enabled Decarboxylative
Borylation of Aryl N-Hydroxyphthalimide Esters. J. Am. Chem.
Soc. 2017, 139, 7440-7443; (e) Zhang, L.-S.; Chen, G.; Wang, X.;
Guo, Q.-Y.; Zhang, X.-S.; Pan, F.; Chen, K.; Shi, Z.-J., Direct
Jia Tang − College of Chemistry and Chemical Engineering,
Southwest Petroleum University, Xindu Road 8, Chengdu, Si-
chuan 610500, China
Thishana Singh − College of Agriculture, Engineering and Sci-
ence, School of Chemistry and Physics, University of KwaZulu-
Natal, Durban 4000, South Africa
Xingzhen Li − College of Chemistry and Chemical Engineering,
Southwest Petroleum University, Xindu Road 8, Chengdu, Si-
chuan 610500, China
Linpeng Liu − College of Chemistry and Chemical Engineering,
Southwest Petroleum University, Xindu Road 8, Chengdu, Si-
chuan 610500, China
Complete contact information is available at:
by Palladium Catalysis. Angew. Chem. Int. Ed. 2014, 53, 3899-
3903.
(7) (a) Xu, L.; Wang, G.; Zhang, S.; Wang, H.; Wang, L.; Liu, L.;
Jiao, J.; Li, P., Recent advances in catalytic C−H borylation
Notes
The authors declare no competing financial interest.
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reactions. Tetrahedron 2017, 73, 7123-7157; (b) Jiang, Z.-T.;
Bridgehead Monophosphine Ligands. J. Am. Chem. Soc. 2011, 133,
19310-19313.
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