Copper-catalyzed reductive borylations on water

Article abstract of DOI:10.1016/j.tet.2017.05.086

In this paper, we established copper catalyzed reductive borylation of terminal alkynes and diboron on water in the presence of amine. Moderate conditions enabled selective borylations of vinyl-substituted phenylacetylenes to undergo the borylation at a C–C triple bond. The Cu catalyst can be recycled for seven times.

Full text of DOI:10.1016/j.tet.2017.05.086

Accepted Manuscript
Copper-catalyzed reductive borylations on water
Chihiro Tanaka, Kimiaki Nakamura, Takashi Nishikata
PII:
S0040-4020(17)30595-1
10.1016/j.tet.2017.05.086
TET 28752
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 April 2017
Revised Date: 25 May 2017
Accepted Date: 28 May 2017
Please cite this article as: Tanaka C, Nakamura K, Nishikata T, Copper-catalyzed reductive borylations
on water, Tetrahedron (2017), doi: 10.1016/j.tet.2017.05.086.
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Copper-catalyzed reductive borylations on
water
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Chihiro Tanaka, Kimiaki Nakamura and Takashi Nishikata
Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi, 755-
8611, Japan.

1
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Tetrahedron
journal homepage: www.elsevier.com
Copper-catalyzed reductive borylations on water
Chihiro Tanaka, Kimiaki Nakamura and Takashi Nishikata
Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi, 755-8611, Japan.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
In this paper, we established copper catalyzed reductive borylation of terminal alkynes and
diboron on water in the presence of amine. Moderate conditions enabled selective borylations of
vinyl-substituted phenylacetylenes to undergo the borylation at a C-C triple bond. The Cu
catalyst can be recycled for seven times.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Copper
Water
Borylation
Recycling
———
Corresponding author. Tel.: +0-000-000-0000; fax: +0-000-000-0000; e-mail: author@university.edu

2
Tetrahedron
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1. Introduction
1-Alkenylboron compounds are very useful and important
reagents for organic synthesis 1,2. In particular, 1-alkenylborons
are an important coupling partner for Suzuki-Miyaura couplings
2. Several synthetic utilities have been developed, whereas their
synthetic approaches have also been well-studied, including
Table 1 Amine effects
3
reaction of alkenyl metal species (Mg or Li) with B(OR)3 , metal
catalyzed hydroborations of alkynes with HBpin (pinacolborane)
4, olefin metathesis 5 and boron Heck reaction 6.
Several approaches mentioned above realized useful synthetic
methodologies, the reactions under sustainable conditions are still
problematic. In this context, reductive borylations are one of the
promising reactions to accomplish sustainable borylations.
Reductive borylation reaction provides a simple protocol to
synthesize 1-alkenylborons, in which terminal alkyne, diboron
and protic solvent require to carry out the reaction 7,8,9. Although
some reports enabled various reductive borylation reactions,
borylation with recycling a catalyst on water has not yet been
established. Water is one of the most attractive medium for
organic synthesis because of safety, economics, and
environmental compatibilities10. In this report, we established
copper-catalyzed reductive borylation on water, in which the
copper catalyst embedded in water can be recycled several times
(Scheme 1).
aAll reactions were carried out on water at 45 ºC for 20 h with CuI (10
mol%), PMDETA (5 mol%), amine (1.5 equiv), 1a (1.0 equiv.) and 2
(2.0 equiv.). Yields were isolated. b Without PMDETA.
Scheme 1. Reductive borylation on water.
2. Results and discussion
Our initial screening shown in Table 1 employed the reaction
of phenylacetylene (1a), bis(pinacolate)diboron (B2pin2), CuI,
PMDETA (N,N,N′,N″,N″-pentamethyldiethylenetriamine), and
amine in water at 45 ºC. In reductive borylation chemistry,
inorganic bases are effective but the reaction in water required an
organic base, such as amine, rather than inorganic bases.
Primary- and tertiary-amines did not gave satisfied yield of 3a.
Table 2 Substrate scope
On
the
other
hand,
secondary-amine,
especially
dicyclohexylamine, gave 72% of 3a in water. Other amines were
also examined but the yields and selectivities were problematic.
The reason for amine effects were not clear. PMDETA ligand
was not important in this reaction and good yield was obtained
without the ligand. We also screened various copper salts, and
ligands but CuI without a ligand was found to be the best catalyst
system in water medium. Recently, Lipshutz reported the metal-
catalyzed reactions in water in the presence of various surfactants
but surfactants were not effective for current reductive
borylation.
Under optimal conditions, we evaluated the reactivities of
alkynes 1 possessing various structures for reductive borylations
in water (Table 2). Generally, reactivities are moderate in water
but fundamental functional groups including methyl, halogen,
and aryl groups resulted in good yields in the presence of 2 or 3
equivalents of diboron (3b-3d, 3f-3h). Interestingly, borylated
substrate gave 3e without loss of the boron moiety.
Heteroaromatic alkynes (3i and 3j) reacted smoothly with
diboron but pyridine substituted alkyne was not effective (3k).
Arylalkynes showed

3
aAll reactions were carried out on water at 45 ºC for 20 h with CuI (10
mol%), Cy2NH (1.5 equiv), 1a (1.0 equiv.) and 2 (2.0 equiv.). Yields
were isolated. b 3 equiv of B2pin2 was used. c Brij (4wt%aq.) was used
as a solvent.
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3. Conclusion
nice reactivities, whereas aliphatic alkynes, such as 1-octyne, did
not give 3l. In this reaction, an internal alkyne or alkene were not
reactive and the corresponding products (3m and 3n) were
obtained in 64% and 70% yield without loss of C-C unsaturated
bonds, respectively. The substrates having CN or ester (3o and
3p) were not reactive on water, because of the solubility problem.
But the reactions in the presence of surfactant such as Brij 35
(Polyoxyethyleneglycol dodecyl ether) gave good yields of the
products.
In conclusion, we have established the Cu-catalyzed reductive
borylation on water. Various substrates were able to be applied to
the reaction system. The reactivities were moderate but this was
effective to carry out selective borylation of alkynes having
unsaturated C-C bonds. Recycling of the catalyst was also
possible on water.
4. Experimental section
4.1 General
Overall, our borylation reactivities were moderate but this
moderate reactivities were effective to undergo the selective
borylation with vinyl substituted alkynes (m-1 and p-1 in Scheme
2)11. Under the optimal conditions, borylations occurred
selectively at C-C triple bond in each substrates.
All reactions were carried out under nitrogen (99.95%)
atmosphere. For TLC analyses precoated Kieselgel 60 F254
plates (Merck, 0.25 mm thick) were used; for column
chromatography Silica Flash® P60 (SiliCycle, 40-63 ꢀm) was
1
used. Visualization was accomplished by UV light (254 nm), H
and 13C NMR spectra were obtained using a JEOL 400 MHz
1
NMR spectrometer. Chemical shifts for H NMR were described
in parts per million (chloroform as an internal standard δ = 7.26)
in CDCl3, unless otherwise noted. Chemical shifts for 13C NMR
were expressed in parts per million in CDCl3 as an internal
standard (δ = 77.16), unless otherwise noted. High resolution
mass analyses were obtained using an ACQUITY UPLC/ TOF-
MS for ESI.
Scheme 2. Selective borylations.
4.2 General procedure for the reductive borylations
Our protocol on water is useful to carry out one-pot reaction and
recycling of catalyst. 1-Alkenylboron is a good Suzuki coupling
pater. After the first borylation to form 3a, second Suzuki
coupling reaction smoothly occurred to produce 6 in 98% yield
(Scheme 3).
CuI (10 mol%), 1 (1 equiv, 0.5 mmol), and 2 (2 equiv, 1.0 mmol)
were sequentially added under air to a dram vial equipped with a
stir bar. Amine (1.5 equiv, 0.75 mmol), and distilled water (1.0
mL) were added by syringe, and the resulting mixture was
vigorously stirred under nitrogen atmosphere [charged by general
N2 (99.95%) gas flow] for 20 h at the temperature, as shown in
the tables. After this time, the contents of the flask were extracted
with ethyl acetate and then concentrated by rotary evaporation.
The residue was purified by flash chromatography, eluting with
hexane/EtOAc to afford the product 3.
4.2.1. (E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane (3a)12
Scheme 3. One-pot process.
Following the general procedure above, using 1a (0.5 mmol),
B2Pin2 (254 mg, 1.0 mmol), CuI (9.5 mg, 0.05 mmol), and
Cy2NH (136 mg, 0.75 mmol), and H2O (1.0 mL) at 45 °C for 20
Our final goal is to establish catalyst recycling system on water
(Table 3). Our recycling is very simple. After the borylation
reaction, the product 3a was extracted with ethyl acetate. After
that, substrates (1 and 2) were added to the water. We tested the
reaction for seven times but the yields were gradually dropped at
each reaction. Especially, the yield was dramatically decreased at
6th reaction. The problem for recycling of catalyst is extraction
process. After the reaction, the product was extracted with ethyl
acetate, but the surface was not clear due to the generation
boronic acid-related salts. Therefore, a part of catalyst in water
was extracted.
1
h, yielded the product 3a (72%); Yellow oil; H NMR (500
MHz, CDCl3) δ: 1.31 (s, 12H), 6.17 (d, J = 18.5 Hz, 1H), 7.28
(dd, J = 1.3 and 8.2 Hz, 1H), 7.33 (dd, J = 1.3 and 8.2 Hz, 2H),
7.40 (d, J = 18.5 Hz, 1H), 7.49 (dd, J = 1.3 and 7.3 Hz, 2H); 13
C
NMR (125 MHz, CDCl3) δ: 24.86, 83.43, 127.20, 128.71,
129.05, 137.60, 149.68.
4.2.2.(E)-4,4,5,5-tetramethyl-2-(4-methylstyryl)-1,3,2-
dioxaborolane (3b)12
Following the general procedure above, using 1b (0.5 mmol),
B2Pin2 (254 mg, 1.0 mmol), CuI (9.5 mg, 0.05 mmol), and
Cy2NH (136 mg, 0.75 mmol), and H2O (1.0 mL) at 45 °C for 20
Table 3. Recycling of catalyst.
1
h, yielded the product 3b (74%); Yellow solid; m.p. 55-56ºC; H
NMR (500 MHz, CDCl3) δ: 1.31 (s, 12H), 2.34 (s, 3H), 6.11 (d, J
= 18.5 Hz, 1H), 7.14 (d, J = 8.6 Hz, 2H), 7.37 (d, J = 18.5 Hz,
1H), 7.39 (d, J = 8.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ:
21.39, 24.88, 83.38, 127.18, 129.45, 134.95, 139.12, 149.66.
4.2.3. (E)-4,4,5,5-tetramethyl-2-(3-methylstyryl)-1,3,2-dioxabo-
rolane (3c)

4
Tetrahedron
1
Yellow oil; IR (neat) ν 2976, 1623, 1378 cm-1; H NMR (500
4.2.10. (E)-4,4,5,5-tetramethyl-2-(2-(thiophen-3-yl)vinyl)-1,3,2-
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MHz, CDCl3) δ: 1.31 (s, 12H), 2.34 (s, 3H), 6.15 (d, J = 18.5 Hz,
1H), 7.11 (d, J = 7.0 Hz, 1H), 7.23 (t, J = 7.8 Hz, 1H), 7.30 (d, J
= 6.8 Hz, 2H), 7.37 (d, J = 18.5 Hz, 1H); 13C NMR (125 MHz,
CDCl3) δ: 21.41, 24.84, 83.36, 124.36, 127.90, 128.59, 129.85,
137.59, 138.19, 149.84; HREIMS calcd. for C15H22BO2 (M+H+):
245.1712; found 245.1713.
d-ioxaborolane (3j) 12
Yellow oil; 1H NMR (500 MHz, CDCl3) δ: 1.30 (s, 12H), 5.94 (d,
J = 18.3 Hz, 1H), 7.27 (dd, J = 0.5 and 2.8 Hz, 1H), 7.29 (d, J =
1.3 Hz, 1H), 7.31 (dd, J = 1.4 and 2.8 Hz, 1H) 7.38 (d, J = 18.3
Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 24.85, 83.40, 125.02,
125.16, 126.27, 141.37, 143.32.
4.2.4.
(E)-2-(4-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-
4.2.11. (E)-4,4,5,5-tetramethyl-2-(4-(oct-1-yn-1-yl)styryl)-1,3,2-
dioxaborolane (3m)
dioxaboro-lane (3d)6
Yellow solid; m.p. 90-91ºC; 1H NMR (500 MHz, CDCl3) δ: 1.31
(s, 12H), 6.14 (d, J = 18.3 Hz, 1H), 7.30 (d, J = 8.3 Hz, 2H), 7.37
(d, J = 18.3 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H); 13C NMR (125
MHz, CDCl3) δ: 24.90, 83.61, 128.42, 128.98, 134.80, 136.14,
148.23.
1
Yellow oil; IR (neat) ν 3289, 2976, 2105, 1620 cm-1; H NMR
(500 MHz, CDCl3) δ: 0.90 (t, J = 7.4 Hz, 3H), 1.26-1.36 (m, 4H),
1.31 (s, 12H), 1.41-1.47 (s, 2H) 1.56-1.62 (m, 2H), 2.40 (t, J =
7.4 Hz, 3H), 6.14 (d, J = 18.5 Hz, 1H), 7.33-7.40 (m, 4H); 7.37
(d, J = 18.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 14.15,
19.59, 22.65, 24.89, 28.70, 28.78, 31.46, 80.69, 83.52, 92.06,
124.78, 127.04, 131.93, 136.69, 148.97; HREIMS calcd. for
C22H32BO2 (M+H+): 339.2495; found 339.2495.
4.2.5. (E)-4,4,5,5-tetramethyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dio-
xaborolan-2-yl)styryl)-1,3,2-dioxaborolane (3e)
Colorless solid; m.p. 210-211ºC; IR (neat) ν 2978, 1622, 961 cm-
1;1H NMR (500 MHz, CDCl3) δ: 1.31 (s, 12H), 1.33 (s, 12H),
6.23 (d, J = 18.5 Hz, 1H), 7.40 (d, J = 18.5 Hz, 1H), 7.48 (d, J =
18.5 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.77 (d, J = 8.3 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ: 24.89, 24.94, 83.51, 83.94,
126.48, 135.19, 140.18, 149.56; HREIMS calcd. for C20H31B2O4
(M+H+): 357.2408; found 357.2403.
4.2.12. (E)-4,4,5,5-tetramethyl-2-(4-(prop-1-en-2-yl)styryl)-1,3,2-
dioxaborolane (3n)
Yellow oil; IR (neat) ν 3084, 2975, 1602 cm-1; 1H NMR (500
MHz, CDCl3) δ: 1.31 (s, 12H), 2.15 (s, 3H), 5.09 (s, 1H), 5.41 (s,
1H), 6.16(d, J = 18.4 Hz, 1H), 7.39 (d, J = 18.4 Hz, 1H), 7.45 (s,
4H); 13C NMR (125 MHz, CDCl3) δ: 21.74, 24.89, 83.46, 112.95,
125.82, 127.14, 136.76, 136.76, 141.77, 149.23; HREIMS calcd.
for C17H24BO2 (M+H+): 271.1869; found 271.1865.
4.2.6. (E)-2-(2-fluorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lane (3f)13
Yellow oil; 1H NMR (500 MHz, CDCl3) δ: 1.31 (s, 12H), 6.24 (d,
J = 18.0 Hz, 1H), 7.02 (dd, J = 1.2 and 8.3 Hz, 1H), 7.11 (dd, J =
0.8 and 7.5 Hz, 1H), 7.25 (m, 1H), 7.57 (dd, J = 1.8 and 7.5 Hz,
1H), 7.60 (d, J = 18.0 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ:
24.88, 83.57, 116 (d, J = 22.1 Hz), 124 (d, J = 3.6 Hz), 125 (d, J
= 11.8 Hz), 127 (d, J = 3.3 Hz), 130 (d, J = 8.6 Hz), 141 (d, J =
4.1 Hz), 160 (d, J = 251 Hz).
4.2.13.
(E)-4-(4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)-vinyl)phenyl)butanenitrile (3o)
Colorless solid; m.p. 98-99ºC; IR (neat) ν 2984, 2945, 2249 1602
cm-1;1H NMR (500 MHz, CDCl3) δ: 1.31 (s, 12H), 2.14 (m, 2H),
2.09 (t, J = 7.1 Hz, 2H), 4.08 (t, J = 5.7 Hz, 2H), 6.02 (d, J = 18.4
Hz,1H), 6.85 (d, J = 8.6 Hz, 2H), 7.34 (d, J = 18.4 Hz, 1H), 7.42
(d, J = 8.8 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ: 14.22, 24.86,
25.48, 65.33, 83.30, 114.55, 119.20, 128.57, 130.95, 148.90,
159.06; HREIMS calcd. for C18H25BNO2 (M+H+): 298.1978;
found 298.1979.
4.2.7. (E)-2-(2-([1,1'-biphenyl]-2-yl)vinyl)-4,4,5,5-tetramethyl-
1,3,2-dioxaborolane (3g)
1
Yellow oil; IR (neat) ν 3058, 2975, 1616 cm-1; H NMR (500
MHz, CDCl3) δ: 1.25 (s, 12H), 6.12 (d, J = 18.2 Hz, 1H), 7.31 (d,
J = 4.5 Hz, 1H), 7.30-7.31 (m, 1H), 7.34-7.43 (m, 9H); 13C NMR
(125 MHz, CDCl3) δ: 24.84, 83.34, 126.67, 127.28, 127.64,
128.22, 128.68, 130.13, 130.47, 136.20, 140.75, 141.66, 148.78;
HREIMS calcd. for C20H24BO2 (M+H+): 307.1869; found
307.1871.
4.2.14. Methyl (E)-4-(4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lan-2-yl)vinyl)phenyl)butanoate (3p)
Yellow solid; m.p. 66-67ºC; IR (neat) ν 2978, 1730, 1617, 1511,
1
1354, 1140, 996, 805 cm-1; H NMR (500 MHz, CDCl3) δ: 1.30
(s, 12H), 2.10 (pent, J = 7.0 Hz, 2H), 2.52 (t, J = 7.2 Hz, 2H),
3.68 (s, 3H), 4.01 (t, J = 6.1 Hz, 2H), 6.00 (d, J = 18.3 Hz, 1H),
6.83 (d, J = 8.7 Hz, 2H), 7.33 (d, J = 18.4 Hz, 1H), 7.41 (d, J =
8.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ: 24.65, 24.88, 30.57,
51.69, 66.75, 83.27, 114.56, 128.53, 130.54, 149.12, 159.61,
173.66; HREIMS calcd. for C19H28BO4 (M+H+): 331.2080; found
331.2083.
4.2.8. (E)-4,4,5,5-tetramethyl-2-(2-(naphthalen-2-yl)vinyl)-1,3,2-
dioxaborolane (3h)
1
Yellow oil; IR (neat) ν 3056, 2974, 1615 cm-1; H NMR (500
MHz, CDCl3) δ: 1.33 (s, 12H), 6.29 (d, J = 18.4 Hz, 1H), 7.45-
7.48 (m, 2H), 7.57 (d, J = 18.4 Hz, 1H), 7.70 (dd, J = 8.9 Hz, J =
1.7 Hz, 1H), 7.79-7.84 (m, 4H); 13C NMR (125 MHz, CDCl3) δ:
24.92, 83.53, 123.57, 126.46, 126.58, 127.87, 128.21, 128.43,
128.60, 133.62, 133.91, 135.17, 149.71; HREIMS calcd. for
C18H22BO2 (M+H+): 281.1712; found 281.1711.
4.2.15. (E)-4,4,5,5-tetramethyl-2-(4-vinylstyryl)-1,3,2-dioxaboro-
lane (p-4)
Yellow oil; IR (neat) ν 2980, 1625 cm-1;1H NMR (500 MHz,
CDCl3) δ: 1.31 (s, 12H), 5.26 (dd, J = 0.6 and 11.0 Hz, 1H), 5.77
(dd, J = 0.7 and 17.7 Hz, 1H), 6.16 (d, J = 18.4 Hz, 1H), 6.70
(dd, J = 10.9 and 17.7 Hz, 1H) , 7.37 (d, J = 18.4 Hz, 1H), 7.38
(d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.2 Hz, 2H); 13C NMR (125
MHz, CDCl3) δ: 24.90, 83.50, 114.46, 126.62, 127.47, 136.58,
137.17, 138.31, 149.20; HREIMS calcd. for C16H22BO2 (M+H+):
257.1712; found 257.1713.
4.2.9. (E)-2-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-4,4,5,5-tetramet-
hyl-1,3,2-dioxaborolane (3i)6
Yellow solid; m.p. 77-78ºC; 1H NMR (500 MHz, CDCl3) δ: 1.30
(s, 12H), 5.95 (d, J = 18.5 Hz, 1H), 5.97 (s, 2H), 6.77 (d, J = 8.1
Hz, 1H), 6.94 (dd, J = 1.6 and 8.1 Hz, 1H), 7.03 (d, J = 1.6 Hz,
1H), 7.29 (d, J = 18.5 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ:
24.87, 83.40, 101.34, 106.01, 108.40, 122.83, 132.34, 148.26,
148.55, 149.20.
4.2.16. (E)-4,4,5,5-tetramethyl-2-(3-vinylstyryl)-1,3,2-dioxaboro-
lane (m-4)

5
Yellow oil; 1H NMR (500 MHz, CDCl3) δ: 1.31 (s, 12H), 5.26 (d,
J = 11.0 Hz, 1H), 5.76 (d, J = 17.5 Hz, 1H), 6.19 (d, J = 18.5 Hz,
1H), 6.70 (dd, J = 11.0 and 17.5 Hz, 1H), 7.31 (d, J = 7.2 Hz,
1H), 7.34 (s, 1H), 7.36 (d, J = 18.5 Hz, 1H), 7.41 (d, J = 9.2 Hz,
1H), 7.52 (s, 1H); 13C NMR (125 MHz, CDCl3) δ: 24.90, 83.52,
114.35, 125.21, 126.59, 126.87, 128.93, 136.78, 137.90, 137.99,
149.52; HREIMS calcd. for C16H22BO2 (M+H+): 257.1712; found
257.1712.
(i) Lipshutz, B. H., Boskovic, Z. V., Aue, D. H. Angew. Chem., Int. Ed.
2008; 47: 10183;
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(j) Obligacion, J. V., Neely, J. M., Yazdani, A. N., Pappas, I, Chirik, P. J.
J. Am. Chem. Soc. 2015; 137: 5855.
5. Morrill, C, Grubbs, R. H., J. Org. Chem. 2003; 68: 6031.
6. Reid, W. B., Spillane, J. J., Krause, S. B., Watson, D. A. J. Am. Chem. Soc.
2016; 138: 5539.
7. Selected Cu catalyzed reductive borylations:
(a) Takahashi, K., Ishiyama, T., Miyaura, N. Chem. Lett., 2000; 982;
(b) Lee, J., Kwon, J, Yun, J. Chem. Commun., 2008; 733;
(c) Kim, H. R., Jung, I. G., Yoo K., Jang K., Lee E. S., Yun, J., Son, S. U.
Chem. Commun., 2010; 46: 758;
4.2.17. Biphenyl (6)14
White solid; m.p. 123ºC; 1H NMR (500 MHz, CDCl3) δ: 7.12 (s,
2H), 7.27 (t, J = 7.4 Hz, 2H), 7.37 (t, J = 7.4 Hz, 4H), 7.53 (dd, J
= 1.4 and 8.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ: 127.4,
128.5, 129.5, 138.22.
(d) Moure A. L., Arrayás R. G., Cárdenas D. J., Alonso I., Carretero J. C.
J. Am. Chem. Soc. 2012; 134: 7219;
(e) Semba K., Fujihara T., Terao J., Tsuji Y. Chem. Eur. J. 2012; 18:
4179;
(f) Catalyst recycling system: Yao, Z., Hong, S., Zhang, W., Liu, M.,
Deng, W. Tetrahedron Lett., 2016; 57: 910;
(g) Zhou, X., Sun, Y., Wu, Y., Dai, J., Xu, J., Huang, Y., Xu, H.
Tetrahedron. 2016; 72: 5691;
Acknowledgement
Financial support provided by program to disseminate tenure
tracking system, MEXT, Japan and the Sasakawa Scientific
Research Grant from The Japan Science Societyis gratefully
acknowledgement.
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Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2017.03.074.
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