Aryl and heteroaryl nosylates as stable and cheap partners for Suzuki-Miyaura cross-coupling reactions

Article abstract of DOI:10.1016/j.tet.2016.02.061

Aryl and heteroaryl para-nitrophenylsulfonates (nosylates) have been successfully engaged for the first time in Suzuki-Miyaura cross-coupling reactions with various aryl or vinylboronic acids (48-98%, 12 examples). The best catalyst/ligand combination have been determined to be 2 mol % of palladium acetate (Pd(OAc)₂) and 4 mol % of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos) using K₃PO₄ as base, in tetrahydrofuran at 80 °C. These new reaction conditions notably provide a direct and very efficient access to the natural alkaloid dubamine.

Full text of DOI:10.1016/j.tet.2016.02.061

Tetrahedron 72 (2016) 1960e1968
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Aryl and heteroaryl nosylates as stable and cheap partners for
SuzukieMiyaura cross-coupling reactions
Anna Dikova, Nicolas P. Cheval, Aur eꢀ lien Blanc, Jean-Marc Weibel , Patrick Pale *
*
Laboratoire de Synth ꢁe se, R ꢀe activit ꢀe Organiques et Catalyse, Institut de Chimie, UMR 7177 e CNRS, Universit ꢀe de Strasbourg, 4 rue Blaise Pascal, 67070
Strasbourg, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Aryl and heteroaryl para-nitrophenylsulfonates (nosylates) have been successfully engaged for the first
time in SuzukieMiyaura cross-coupling reactions with various aryl or vinylboronic acids (48e98%, 12
examples). The best catalyst/ligand combination have been determined to be 2 mol % of palladium ac-
Received 22 December 2015
Received in revised form 25 February 2016
Accepted 26 February 2016
Available online 2 March 2016
0
0
0
etate (Pd(OAc)
PO
2
) and 4 mol % of 2-dicyclohexylphosphino-2 ,4 ,6 -triisopropylbiphenyl (XPhos) using
ꢀ
K
3
4
as base, in tetrahydrofuran at 80 C. These new reaction conditions notably provide a direct and
very efficient access to the natural alkaloid dubamine.
Keywords:
Ó 2016 Elsevier Ltd. All rights reserved.
Nosylates
Aryl
Palladium
Cross-coupling reaction
SuzukieMiyaura
1
. Introduction
of natural products, mostly known for their interesting pharma-
7
6
ceutical and biological activities. In the continuity of our work, we
have investigated in more details the possibilities offered by aryl
and heteroaryl nosylates in SuzukieMiyaura reaction and we now
describe their synthesis and their behavior in such cross-coupling
reactions (Scheme 1).
Metal-catalyzed cross-coupling reactions have become one of
1
the most powerful reactions in organic synthesis. They indeed
allowed to efficiently produce carbonecarbon or carbon-
eheteroatom bonds, under relatively mild conditions especially
with palladium catalysts. Among the developed methods, Suzu-
2
kieMiyaura coupling represents one of the most important,
3
widely used and applied to numerous areas, including industrial
procedures.4
Numerous improvements of the original protocol have been
reported, mostly focusing on the catalyst and the boron reagent.
The electrophilic partner was rather neglected, and halides and
triflates still remain widely used as such. Recently, we showed that
para-nitrophenylsulfonate (Nosylate¼ONs) could successfully re-
Scheme 1. Nosylation-coupling sequence starting from arenes and heteroarenes.
5
place triflates and other sulfonates in the most popular palladium-
Arenes and heteroarenes are indeed common motif in natural
products, as well as important classes of compounds in pharma-
catalyzed cross-couplings, e.g., SuzukieMiyaura, Stille, Mizoroki-
6
Heck and Sonogashira reactions. Nosylates are solid, often crys-
4,8
ceutical and material sciences. They are often produced by cross-
talline reagents, very stable, easily storable, especially compared to
triflates.
In our previous work, we essentially focused our interest on the
preparation of 4-arylcoumarins, the so-called neoflavonoids family
coupling reactions, especially the SuzukieMiyaura reaction
Scheme 2).
(
2
2
. Results and discussion
.1. Aryl nosylate formation
*
Corresponding authors. Tel.: þ33 368 851517 (P.P.); tel.: þ33 368 851586
J.-M.W.); e-mail addresses: jmweibel@unistra.fr (J.-M. Weibel), ppale@unistra.fr
P. Pale).
Aryl sulfonates are routinely prepared by sulfonylation of the
corresponding phenols under basic conditions. Depending on the
(
(
http://dx.doi.org/10.1016/j.tet.2016.02.061
040-4020/Ó 2016 Elsevier Ltd. All rights reserved.
0

A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
1961
Table 1
Nosylation of aryl and heteroaryl derivatives
Entry
Product
Conditiona,b,c
Time(h)
Yield (%)d
1
2
3
1a
1b
1c
1d
1e
1f
A
B
C
1
1
1
53
84
98
Scheme 2. A few examples of natural products, pharmaceuticals and useful com-
pounds containing arene motif (The highlighted CeC bonds in red denote the key
coupling reaction which have been used to prepare them).
52e
63
79
4
5
6
A
16
2
7
f
B
C
pKa and sensitivity of the compounds, weak inorganic base such as
carbonates or strong base such as sodium hydride, lithium amides,
could be used. For the introduction of the nosyl group, we relied on
both methods and we also explored the mild conditions we used
for preparing vinyl nosylates, e.g., H u€ nig’s base in dichloromethane
at room temperature (Table 1; conditions A, B and C, respectively).
All methods gave within 30 min to 2 h at room temperature the
expected nosylates in good to quantitative yields, except for a few
cases. For aryl derivatives, the use of H u€ nig’s base (condition C)
7
8
9
A
B
C
2
1
1
98
73
98
10
1
1
A
B
C
2
1
1
71
77
87
1
2
was overall more effective than any other conditions (A or B) with
a 92% average yield. The use of potassium carbonate (condition A)
and NaH deprotonation (condition B) gave similar results with,
respectively, 73 and 78% average yields. Under condition C, re-
actions were always fast (ꢁ1 h), except for hindered substrates
13
1
1
A
B
C
3
4
3
67
76
88
4
5
1
1
6
7
A
B
1
1
85
87
(
entries 6 and 24). For heteroaryl derivatives, no clear trend could
18
C
1
95
be observed and each case seemed specific (see below). The
overall results nevertheless confirmed that these reactions are
mostly driven by the balance between acidity and nucleophilicity
of the phenol moiety depending on the conditions and thus the
solvation.
1
2
2
9
0
1
1g
1h
A
B
C
1
1
1
82
93
97
Interestingly, hindered phenols, such as o,oʹ-dimethylphenol
2
2
2
3
A
16
1
84
85
(
entries 4e6) and 1,1ʹ-bi-2-naphthol (BINOL) (entries 22e24), could
f
B
be converted to the corresponding nosylates 1b and 1h in good to
high yields. Nevertheless, the deprotonation method (condition B)
required slightly higher temperatures in these cases (entries 5 and
24
C
7
96
2
3). Furthermore, all these nosylation conditions were compatible
with various functional groups (entries 7e15, 25e35), including
reactive ones, as shown with the very efficient and even quantita-
tive formation of nosylates 1ced from the 4-acetyl- and for-
mylphenols (entries 7e9 and 10e12).
2
5
1i
1j
C
1
88
The nosylation of pyridinols and quinolinol was less trivial
(
entries 27e35). Although 3-hydroxypyridine afforded the desired
nosylate 1k in high to quantitative yields with each method (entries
7e29), its isomeric 2-hydroxypyridine gave a mixture of O- and N-
26
C
1
96
2
9
nosylated products, as reported for its tosylation. The ratio be-
tween these two nosylation products varied between 2:1 to 9:1 in
favor of the O-nosylated product 1l depending on the conditions
used (entries 30e32). Condition A with potassium carbonate as
base provided the best yield of the expected O-nosylate 11 while
minimizing the N-nosylate formation (respectively, 65 and 8%,
entry 30). Both isomers could nevertheless be easily separated by
chromatography. 2-Hydroxyquinoline could only be transformed
efficiently into its nosylate 1m with sodium hydride under slightly
modified conditions (entry 34).
2
28
7
1k
1l
A
B
C
0.5
1
1
99
70
96
29
30
31
A
0.5
65g
g
B
C
1
1
57
58
g
32
(
continued on next page)
This nosylation reaction proved to be robust, versatile and
scalable, providing up to 5 g batch (compounds 1a, 1c, 1d, 1f, 1g and
1
h), with purification by crystallization in all cases.

1962
A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
Table 1 (continued )
Entry Product
Table 2
Conditions screening for the SuzukieMiyaura coupling of aryl nosylate 1ca
Conditiona,b,c
Time(h)
7 d.
Yield (%)d
19
33
1m
A
h
3
3
4
5
B
1
16
75
27
C
ꢀ
Yield (%)b
a
b
c
Entry
Ligand
Base
T ( C)
Time (h)
Conditions A: K
Conditions B: NaH (1.25 equiv), NsCl (1.05 equiv), THF (0.5M), 30 C.
Conditions C: NEtiPr (1.2 equiv), NsCl (1.05 equiv), CH Cl (0.125M), rt.
2 3
CO (1.8 equiv), NsCl (1.1 equiv), MeCN (0.1M), rt.
ꢀ
1
2
3
4
d
K
2
K
2
K
3
”
CO
CO
3
80
80
”
20
20
”
0
0
”
3
Ph P
”
3
2
2
2
d
e
f
Yields of isolated pure products.
Incomplete conversion.
PO
4
(o-Tol)
3
P
80
20
0
ꢀ
Performed at 50 C.
g
h
The N-nosyl pyridinone was also isolated (8, 26 and 32%, respectively).
Slow addition of a THF solution of NsCl (1M) over 20 min.
PCy
OMe
2
MeO
5
K
3
PO
4
80
21
Traces
2
.2. SuzukieMiyaura coupling of aryl and heteroaryl
nosylates
(SPhos)
It is well established that aryl triflates are less reactive than vinyl
triflates, due to a less easy oxidative addition. In this context, it
10
PCy2
was not so surprising that the coupling conditions we already set
up earlier (boronic acid, PdCl (dppf) as catalyst in the presence of
2
6
7
K
3
3
PO
4
4
80
80
21
21
Traces
(
2
Cy JohnPhos)
aqueous solution of potassium carbonate in THF at room temper-
6
ature) did not promote any coupling, even at higher temperature.
P(tBu)
2
These results forced us to develop a specific coupling procedure for
aryl nosylates.
K
PO
27
In our earlier work,6 a catalyst screening revealed that palla-
dium diacetate, in the presence of aqueous solution of potassium
(JohnPhos)
carbonate in THF, was the second best catalyst after PdCl
2
(dppf)
(
respectively, 85 vs 95% yield starting from 4-coumarinyl nosylate).
We therefore started another screening with this simple and stable
palladium salt as catalyst (Table 2) and we selected the 4-
acetylphenyl nosylate 1c and the simplest phenylboronic acid 2a
as model.
P(tBu)2
iPr
iPr
8
K
3
PO
4
1
Traces
iPr
Palladium diacetate itself was unable to promote the reaction
entry 1), but fortunately, this salt in combination with mono-
dentate phosphines gave interesting and useful results. Simple
aryl phosphine ligands did not provide catalysts reactive enough
for this coupling reaction, even upon prolonged heating (entries
(
tBuXPhos)
(
OMe
MeO
iPr
PCy
iPr
2
9
K
3
PO
4
80
30
2
41c
18
2
e4). Widely used in various Pd-catalyzed cross-coupling re-
11
actions, especially SuzukieMiyaura reaction, biaryl ligands
iPr
were investigated in this particular coupling (entries 5e12).
Known for its high efficiency in the presence of potassium
(BrettPhos)
12
10d
Aq K CO3
22
phosphate, even at low loading, SPhos was examined but
without success (entry 5). Usually also quite effective, the simple
JohnPhos-type ligands gave disappointing results (entries 6e7).
Nevertheless, JohnPhos was able to induce some product for-
mation, but only in low yield (entry 7). Since bulkier ligands
seemed to promote the reaction, we examined the behavior of
a few others (entries 8e12). tBuXPhos was however probably too
bulky (entry 8), while BrettPhos gave interesting results within
short reaction time (entry 9), probably as a good compromise
2
PCy
iPr
2
1
1
1
2
K
K
2
CO
PO
3
80
80
2
2
56
93
iPr
3
4
iPr
(XPhos)
a
Conditions: substrate (1 equiv), PhB(OH)2 (2 equiv), Pd(OAc)2 (2 mol %), L (4 mol
%) and base (2.8 equiv) in THF (0.17M).
between bulkiness and the stabilizing effect of ortho-alkoxy
b
substituent.13 Despite the lack of the latter effect, XPhos turned
Yields of isolated pure products.
Determined by NMR of the crude residue with hexamethylbenzene as internal
c
out to be the best choice, allowing to afford the coupling product
in excellent yield in the presence of potassium phosphate (entry
standard.
d
Performed with a 2M solution.
12). Adjusting the base nature proved deleterious rather than
improving further the reaction (entries 10e11 vs 12). It is worth
noting that we also isolated 3e5% of homocoupling product of
boronic acid in those reactions.
Having established the optimum reaction conditions (Table 2,
entry 12), we next evaluated the scope and limitation of (hetero)
aryl nosylates in this SuzukieMiyaura coupling. We first in-
vestigated the coupling of the 4-acetylphenyl nosylate 1c with
various boronic acids (Table 3). With the same starting product, the
oxidative addition step should be the same and thus this series
should provide information about the last steps of the catalytic
cycle.
When boronic acid carried halogenated electron-withdrawing
groups at various positions, no reaction occurred despite pro-
longed reaction times (entries 2e3). Less deactivated, the phenyl-
boronic acid with a para-carboxylate group 2d readily reacted,

A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
1963
Table 3
special ligand known to be flexible and thus particularly favorable
for bulky coupling partner (Scheme 3, top). Vinylboronic acids
could also be engaged in this coupling reaction, as shown with 2h.
The coupling nevertheless required several hours and only mod-
erate yields could be achieved (entry 8).
Scope of the formation of biaryls 3 from 4-acetylphenyl nosylate 1c and boronic
13
a
acids
Entry
1
Boronic acid
Product
Time (h) Yield (%)b
2
23
70
93
2
d
d
n.r.c
n.r.c
Scheme 3. Possible conformers upon oxidative addition of Pd(XPhos) complex to aryl
nosylates (top; Rʹ¼Ns), and possible transmetalation step (bottom; Rʹ¼Ns or H).
3
4
These results tend to overall follow the classical trends of re-
ductive elimination, except for bulkiness. The latter might in turn
limit the transmetalation step, due to the large ligand used. This
effect would be particularly preeminent with the nosylate still co-
1.5
93
14
ordinated to palladium during this step (Scheme 3, bottom).
We then next examined the coupling of various aryl and het-
eroaryl nosylates with phenylboronic acid (Table 4). This series
should provide some hints about the oxidative addition to
nosylates.
Compared to the simplest phenyl nosylate 1a, phenyl nosylates
carrying electron-withdrawing groups were efficiently coupled
within a few hours, giving the corresponding biaryls in high yields
5
6
1.5
1.5
98
95
(Table 3, entry 1 and Table 4, entry 2 vs 1). However, with an
electron-donating group, the nosylate 1e did not react despite
prolonged reaction time (entry 3). This lack of reaction was also
observed for the hindered o,oʹ-dimethylphenyl nosylate 1b (entry
4). If the former results correspond to the known pattern of oxi-
dative addition, the latter result could be again accounted for steric
hindrance at the oxidative addition step, corroborating the results
gained from the coupling of 1c with 2g (Table 3, entry 7). It is
noteworthy that the coupling of the 4-formylphenyl nosylate 1d led
to the formation of a side-product, which slowly accumulated over
time (13% isolated yield after 21 h) to the detriment of the coupling
product (entry 2). This compound resulted from the addition of
boronic acid to the formyl group of the coupling product 3k, as
7
8
d
21
n.r.c
49
9
15
already observed in related reaction.
Overall, the reactivity trend gained from these results corre-
sponds to the known pattern of oxidative addition.
a
Conditions: substrate (1 equiv), RB(OH)
PO
Yields of isolated pure material.
2
(2 equiv), Pd(OAc)
4
(2.8 equiv) in THF (0.17M).
2
(2 mol %), XPhos
(
4 mol %) and K
3
Naphthyl nosylates readily gave the coupling products, although
b
c
the reaction required several hours to proceed. The
efficiently converted to the expected product than the
tatively yielding 2-phenylnaphtalene (entry 5 vs 6). This difference
could also be due to steric problems, the inducing less strain than
the upon oxidative addition. Possibly for similar reasons, the
b
was more
No reaction, starting material recovered.
a, quanti-
b
giving the expected biaryl 3d slightly more rapidly than the simple
phenylboronic acid (entry 4 vs 1). Similar yields were obtained for
both. As expected, phenylboronic acids carrying electron-donating
group were very reactive and the corresponding biaryls 3eef were
isolated in excellent or quantitative yields (entries 5e6), except for
the ortho-methyl derivative 2g, which did not react. Since the an-
alog methoxy substituted 2f was reactive, steric hindrance might be
responsible for this lack of reaction, due to the presence of a methyl
group adjacent to the reactive site and despite the presence of
a
bisnosylate 1h derived from binol led to a complex mixture of
mono- and dicoupling products, as well as starting material (entry
7). It was indeed been shown that significant distortion is required
16
for the oxidative addition to proceed, especially with triflate.
Interestingly, the 4-chloro- and 4-bromonaphtyl nosylate 1iej
reacted with phenylboronic acid but both at the halo position and
not at the nosyl one, providing the 4-phenylnaphtyl nosylate 3m in
high yields (entries 8e9). Being in a para position, the nosylate

1964
A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
Table 4 (continued)
Entry Nosylates
Product
Time(h) Yield (%)b
Table 4
Scope of the formation of biaryls 3 from phenylboronic acid 2a and various aryl
nosylates 1a
13
20i
90
a
Conditions: substrate (1 equiv), RB(OH)
2
(2 equiv), Pd(OAc)
2
(2 mol %), XPhos
(4 mol %) and K
3
PO (2.8 equiv) in THF (0.17M).
4
Entry Nosylates
Product
Time(h) Yield (%)b
b
Yields of isolated pure products. Homocoupling product was always detected by
TLC analysis, but when isolated with less than 5%.
c
Boronic acid, catalyst and ligand loadings doubled.
1
16
61
d
Starting material recovered.
e
f
0
1,1 -Biphenyl-4-yl) (phenyl)methanol forms as a side product.
(
Complex mixture.
Performed with p-MeOPhB(OH) .
2
Conditions: Substrate (1 equiv), PhB(OH)
g
h
2
(2 equiv), Pd(OAc)
2
(2 mol %), XPhos
2
2
6
1
71
78
64
ꢀ
e
e
(4 mol %), NaOH (1.7 equiv) in nBuOH/H
2
O (4/1, 0.14M) at 30 C.
i
2
Pd(OAc) (4 mol %) and XPhos (8 mol %) are used.
2
group in 1iej could act as a strong electron-withdrawing group
relative to the “para”-halo substituent and thus activate the latter
position. However, such reversed reactivity has already been no-
n.r.d
3
4
5
d
d
20
40c
16
17
ticed, whatever the relative position of the groups. Furthermore,
the halide versus triflate selectivity seemed specific to Suzu-
n.r.d
98
18
kieMiyaura coupling reaction. Since it has been observed that the
use of a bulky monophosphine favored the displacement of chlo-
16,17b
ride relative to triflate,
the present conditions based on bi-
phenyl monophosphine might favor such selectivity.
The aryl nosylate 3m, selectively formed (entry 8 and 9), was
engaged in a subsequent cross-coupling reaction affording com-
pound 3n in high yield (entry 10).
Heteroaromatic nosylates containing pyridine motifs gave the
corresponding coupling product with phenylboronic acid, but with
variable yields depending on their structure (entries 11e13). In the
examined series, the 2-quinolyl nosylate 1m was the most reactive,
cleanly providing the corresponding coupling product 3q in high
yield (entry 13). It is worth mentioning that the coupling of this
nosylate 1m with boronic acids provided a direct access to a family
of natural alkaloid products. For example, dubamine 3r, which was
isolated from various plants Dictamnus angustifolius, Haplophylum
dubium, H. latifolium, was produced in high yield upon coupling
with 3,4-(methylenedioxy) phenylboronic acid (Scheme 4).
6
16
40c
18
91
f
7
8
BINOL-Ns 1h
d
d
19
72
9
3m
18
16
71
10
98g
Scheme 4. A short synthesis of the alkaloid dubamine.
1
1
2
18
Traces
”
3
. Conclusion
f
18
In summary, we have developed a straightforward and rapid
access to various aryl and heteroaryl nosylates 1 from the corre-
sponding phenols or hydroxy-substituted heteroarenes. With more
than 10 examples, some of them performed on multigram scale,
with yields often higher than 90%, this nosylation proved to be
robust and valuable. The corresponding nosylates could be coupled
with various boronic acids, usually in good to high yields in the
presence of the simple catalyst Pd(OAc)2 and XPhos, respectively, at
1
18
Traces
48
h
18

A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
1965
2
mol % and 4 mol % loading. This sequence thus provides a conve-
CH
10 min of stirring, a solution of 4-nitrobenzenesulfonyl chloride
(1.05 equiv) in CH Cl (5 mL/mmol) was added. The reaction mix-
ture was then stirred at room temperature under inert atmosphere
for 30 min to 1 h. The reaction was quenched by addition of HCl 1M.
2 2
Cl (3 mL/mmol) at room temperature under argon. After
nient access to a variety of aryl and heteroaryl derivatives from
readily available starting materials and through the very stable,
easily storable nosylate coupling partners.
2
2
4
4
. Experimental section
After extraction with CH
2
Cl
2
(3 times), the combined organic layers
were dried over Na SO
2
4
, and evaporated in vacuo. The crude was
.1. General information
triturated in EtOH and then filtered. The pure product was obtained
by recrystallization in EtOH.
Proton ( H NMR) and Carbon (13C NMR) nuclear magnetic res-
1
onance spectra were recorded on the following 300, 400 or
00 MHz instruments. The chemical shifts are given in part per
million on the delta scale. The solvent peak was used as reference
4.2.1. Phenyl 4-nitrobenzenesulfonate (1a). Yield: Conditions A: 53%
(151 mg); Conditions B: 84% (4.69 g); Conditions C: 98% (701 mg). H
1
5
NMR (500 MHz, CDCl
3
) d 6.96e7.02 (m, 2H), 7.27e7.36 (m, 3H), 8.03
1
13
13
values. For
CDCl
H
NMR: CHCl
3
¼7.26 ppm. For
C
NMR:
(d, J¼8.9 Hz, 2H), 8.37 (d, J¼8.9 Hz, 2H); C NMR (125 MHz, CDCl
3
)
3
¼77.16 ppm. Data are presented as follow; chemical shift,
d
122.2, 124.5, 127.9, 130.0, 130.1, 141.1, 149.3, 151.1. The product ex-
2
0
multiplicity (s¼singlet, d¼doublet, t¼triplet, q¼quartet,
quint¼quintet, m¼multiplet, b¼broad), coupling constants (J/Hz)
and integration. IR spectra were recorded as neat sample on
a Brucker Alpha spectrophotometer. High-resolution mass spectra
hibitsspectroscopicdataidenticaltothosereportedintheliterature.
4.2.2. 2,6-Dimethylphenyl 4-nitrobenzenesulfonate (1b). Yield:
Conditions A: 52% (261 mg); Conditions B: 63% (3.87 g); Conditions
ꢀ
(
HRMS) were recorded by Electrospray Ionisation (ESI) on an Agi-
C: 79% (2.06 g). Light yellow solid: Mp 112e114 C; IR
n
max 3110,
lent 6520 Accurate Mass Q-TOF. Analytical thin layer chromatog-
raphy (TLC) was carried out on silica gel 60 F254 plates with
visualization by ultraviolet light, para-anisaldehyde or potassium
permanganate dip. Flash column chromatography was carried out
1608, 1531, 1502, 1469, 1452, 1404, 1354, 1306, 1292, 1192, 1170,
ꢂ1
1
1130, 1109, 1079, 861, 848 cm ; H NMR (500 MHz, CDCl
3
) d (ppm)
2.15 (s, 6H), 7.04e7.12 (m, 3H), 8.20 (d, J¼8.8 Hz, 2H), 8.43 (d,
13
J¼8.8 Hz, 2H); C NMR (125 MHz, CDCl
129.5, 129.6, 132.0, 143.0, 147.5, 151.0; HRMS 330.041
SþNa calcd 330.041).
3
) d (ppm) 17.6, 124.6, 127.4,
using silica gel 60 (40e63
mm) and the procedure included the
subsequent evaporation of solvents in vacuo. Reagents and solvents
were purified using standard means. Tetrahydrofuran was dried
using Glasstechnology DryStation ST100 purification system (fil-
tration over alumina) under an argon atmosphere. Acetonitrile,
N,N-diisopropylethylamine (DIPEA) and triethylamine were dis-
(C14H13NO
5
4.2.3. 4-Acetylphenyl 4-nitrobenzenesulfonate (1c). Yield: Condi-
tions A: 98% (3.16 g); Conditions B: 73% (4.69 g); Conditions C: 98%
ꢀ
(7.95 g). Light yellow solid: Mp 102e104 C (ethanol); IR
nmax 3100,
tilled from CaH
reactions were carried out in flame-dried glassware and under an
argon atmosphere. The palladium complex PdCl (dppf)$CH Cl was
purchased from STREM Chemicals. Pd(OAc) and SPhos were pur-
chased from Alfa Aesar. XPhos was purchased from ABCR. JohnPhos,
CyJohnPhos, tBuXPhos and BrettPhos were purchased from Sig-
maeAldrich. All extractive procedures were performed using non-
distilled solvents and all aqueous solutions used were saturated
unless details are given.
2
and stored under an argon atmosphere. Anhydrous
3062, 1679, 1592, 1530, 1405, 1382, 1366, 1350, 1311, 1291, 1260,
1238, 1200, 1174, 1154, 1108, 1012, 870, 852, 826, 767, 737, 681, 664,
ꢂ1
1
2
2
2
633, 618, 585, 553, 527, 464 cm ; H NMR (500 MHz, CDCl
3
) d 2.59
2
(s, 3H), 7.12 (d, J¼8.8 Hz, 2H), 7.94 (d, J¼8.8 Hz, 2H), 8.06 (d,
13
J¼8.7 Hz, 2H), 8.40 (d, J¼8.7 Hz, 2H); C NMR (125 MHz, CDCl
26.8, 122.4, 124.7, 130.0, 130.5, 136.4, 140.8, 151.3, 152.4, 196.5;
HRMS 344.019 (C14
SþNa calcd 344.020).
3
)
d
H11NO
6
4.2.4. 4-Formylphenyl 4-nitrobenzenesulfonate (1d). Yield: Condi-
tions A: 71% (22 mg); Conditions B: 77% (4.73 g); Conditions C: 87%
ꢀ
4
.2. Typical procedure for the nosylation reaction (Table 1)
(3.16 g). White solid: Mp 142e144 C; IR
n
max 3102, 3068, 2853,
2746, 1700, 1610, 1592, 1529, 1496, 1379, 1364, 1348, 1307, 1293,
Conditions A: To a solution of phenolic compound (1 equiv) in
dry acetonitrile (0.1 M) were added successively nitro-
1198, 1169, 1146, 1109, 1090, 1012, 873, 847, 755, 741, 727, 702, 680,
ꢂ1
1
651, 623, 601, 563, 529, 487, 473, 464 cm
CDCl
7.21 (d, J¼8.5 Hz, 2H), 7.88 (d, J¼8.6 Hz, 2H), 8.07 (d,
J¼8.8 Hz, 2H), 8.41 (d, J¼8.8 Hz, 2H), 9.99 (s, 1H); C NMR
(125 MHz, CDCl 123.0, 124.7, 130.0, 131.7, 135.4, 140.7, 151.3,
153.3, 190.5; HRMS 330.004 (C13 NO
SþNa calcd 330.005).
; H NMR (500 MHz,
benzenesulfonyl chloride (1.1 equiv) and potassium carbonate
3
) d
ꢀ
13
(
1.8 equiv). The mixture was then stirred at 30 C under inert at-
mosphere for 30 min to 2 h. The reaction was quenched by addition
of NH Cl satd and diluted with ethyl acetate. After extraction with
ethyl acetate (3 times), the combined organic layers were washed
successively with water and brine, dried over Na SO and con-
3
) d
4
H
9
6
2
4
4.2.5. 4-Methoxyphenyl 4-nitrobenzenesulfonate (1e). Yield: Condi-
centrated under reduced pressure. The pure compound was ob-
tained by precipitation in ether or by chromatography on silica gel
tions A: 67% (745 mg); Conditions B: 76% (376 mg); Conditions C: 88%
1
(2.1 g). H NMR (500 MHz, CDCl
3
)
d
3.78 (s, 1H), 6.80 (d, J¼9.1 Hz,
(
Cyclohexane/Ethyl Acetate).
2H), 6.89 (d, J¼9.1 Hz, 2H), 8.02 (d, J¼8.8 Hz, 2H), 8.37 (d, J¼8.8 Hz,
13
Conditions B: Sodium hydride (NaH 60% dispersion in mineral
2H); C NMR (125 MHz, CDCl
141.1, 142.7, 151.1, 158.7; HRMS 332.0176 (C13
332.0199). The product exhibits spectroscopic data identical to
3
)
d
55.8, 114.9, 123.2, 124.4, 130.1,
oil) (1.25 equiv) was added by portions to a solution of phenolic
compound (1 equiv) in THF (4 mL/mmol). After 15 min of stirring,
a solution of 4-nitrobenzenesulfonyl chloride (1.05 equiv) in THF
H11NO
6
SþNa calcd
2
1
those reported in the literature.
(
4 mL/mmol) was added. The reaction mixture was then stirred
under inert atmosphere at room temperature for 1 h. The reaction
mixture was partitioned between EtOAc and water. The aqueous
layer was extracted with EtOAc (3 times) and the combined organic
4.2.6. Naphthalen-1-yl 4-nitrobenzenesulfonate (1f). Yield: Condi-
tions A: 85% (139 mg); Conditions B: 87% (4.69 g); Conditions C: 95%
ꢀ
(2.41 g). Light brown solid: Mp 160e162 C; IR
n
max 3108, 1608,
layers were dried over Na
2
SO
4
and evaporated under reduced
1598, 1531, 1377, 1346, 1309, 1184, 1164, 1147, 1065, 1032, 1010, 887,
ꢂ1
1
pressure. The crude residue was triturated in EtOH and then fil-
tered. The pure product was obtained by recrystallization in EtOH.
Conditions C: Diisopropylethylamine (DIPEA) (1.2 equiv) was
dropwise added to a suspension of phenolic compound (1 equiv) in
856, 809, 772, 735, 703, 679, 610, 565, 534, 519, 445 cm ; H NMR
(400 MHz, CDCl 7.22e7.29 (m, 1H), 7.36e7.54 (m, 3H), 7.75e7.88
(m, 3H), 8.09 (d, J¼9.0 Hz, 2H), 8.32 (d, J¼8.9 Hz, 2H); C NMR
(125 MHz, CDCl 118.6, 121.2, 124.5, 125.3, 126.9, 127.2, 127.2,
3
) d
13
3
) d

1966
A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
1
27.9, 128.1, 130.0, 134.9, 141.4, 145.4, 151.1; HRMS 352.023
1308, 1205, 1158, 1106, 1087, 1042, 1011, 996, 885, 871, 851, 797,
ꢂ1
1
(
C
16
5
H11NO SþNa calcd 352.025).
759, 744, 736, 724, 678, 620, 603, 553, 495, 468, 428, 413 cm ; H
NMR (500 MHz, CDCl
7.14 (d, J¼8.2 Hz, 1H), 7.25 (ddd, J¼7.4,
4.9, 1.0 Hz, 1H), 7.82 (ddd, J¼8.2, 7.4, 2.0 Hz, 1H), 8.19 (ddd, J¼4.9,
3
) d
4.2.7. Naphthalen-2-yl 4-nitrobenzenesulfonate (1g). Yield: Condi-
13
tions A: 82% (140 mg); Conditions B: 93% (6.13 g); Conditions C: 97%
2.0, 0.6 Hz, 1H), 8.24 (d, J¼8.9 Hz, 2H), 8.39 (d, J¼8.9 Hz, 2H);
NMR (125 MHz, CDCl 115.8, 123.3, 124.3, 130.2, 140.7, 142.8,
148.3, 150.9, 157.0; HRMS 303.002 (C11
C
1
(
1.97 g). H NMR (500 MHz, CDCl
3
)
d
7.09 (dd, J¼8.9, 2.4 Hz, 1H),
3
) d
7
.49 (d, J¼2.4 Hz, 1H), 7.51e7.55 (m, 2H), 7.73e7.87 (m, 3H), 8.06 (d,
H
8
N
2
O
5
SþNa calcd
13
J¼8.9 Hz, 2H); 8.36 (d, J¼9.0 Hz, 2H); C NMR (125 MHz, CDCl
3
)
303.005). 1-((4-Nitrophenyl)sulfonyl)pyridin-2(1H)-one: Isolated as
a side product. Yield: Conditions A: 8% (11 mg); Conditions B: 26%
d
120.0, 120.6, 124.5, 127.0, 127.4, 128.0, 128.0, 130.1, 130.0, 132.2,
1
33.5, 141.1, 146.8, 151.1. The product exhibits spectroscopic data
(88 mg); Conditions C: 32% (125 mg). Light brown solid: Mp
2
2
ꢀ
identical to those reported in the literature.
192e193 C; IR
n
max 3130, 3110, 3084, 1679, 1600, 1530, 1517, 1376,
1
364, 1349, 1312, 1245, 1180, 1124, 1108, 1084, 1021, 1008, 852, 841,
ꢂ1
1
4.2.8. [1,1ʹ-binaphthalene]-2,2ʹ-diyl
bis(4-nitrobenzenesulfonate)
824, 765, 741, 725, 684, 674, 599, 564, 512, 476, 455, 427 cm ; H
NMR (500 MHz, CDCl
(
1h). Yield: Conditions A: 84% (971 mg); Conditions B: 85% (1.67 g);
3
)
d
6.33 (ddd, J¼7.5, 6.4, 1.2 Hz, 1H), 6.44
ꢀ
Conditions C: 97% (4.68 g). White solid: Mp 269e271 C (ethanol);
(ddd, J¼9.3, 1.0, 0.7 Hz, 1H), 7.37 (ddd, J¼9.4, 6.4, 2.0 Hz, 1H), 8.06
(ddd, J¼7.6, 1.8, 0.6 Hz, 1H), 8.31 (d, J¼9.0 Hz, 2H), 8.40 (d,
IR
nmax 3107, 1609, 1591, 1539, 1528, 1508, 1472, 1403, 1381, 1361,
13
1
345, 1314, 1258, 1201, 1175, 1155, 1147, 1133, 1103, 1090, 1068, 1042,
J¼9.0 Hz, 2H); C NMR (125 MHz, CDCl
3
) d 107.2, 123.6, 124.1,
ꢂ1
1
1
013, 967, 938, 902, 879, 868, 853, 824 cm ; H NMR (400 MHz,
CDCl
(ppm) 6.55 (d, J¼8.6 Hz, 2H), 7.06 (ddd, J¼8.3, 7.2, 1.1 Hz,
H), 7.29 (d, J¼8.8 Hz, 4H), 7.34 (ddd, J¼8.2, 7.1, 1.1 Hz, 2H), 7.56 (d,
J¼8.7 Hz, 4H); 7.71 (d, J¼8.1 Hz, 2H), 7.72 (d, J¼9.0 Hz, 2H), 7.93 (d,
131.3, 131.5, 141.9, 141.9, 142.1, 151.3, 160.1; HRMS 303.004
SþNa calcd 303.005).
3
)
d
8 2 5
(C11H N O
2
4.2.13. Quinolin-2-yl 4-nitrobenzenesulfonate (1m). Yield: Condi-
13
J¼9.1 Hz, 2H); C NMR (125 MHz, CDCl
23.4, 126.8, 126.8, 127.4, 128.0, 128.1, 131.0, 131.7, 132.5, 140.9,
45.6, 149.7; HRMS 679.045 (C32
þNa calcd 679.045).
3
)
d
(ppm) 122.4, 122.4,
tions A: 19% (98 mg); Conditions B: 75% (490 mg); Conditions C: 27%
ꢀ
1
1
(205 mg). White solid: Mp 146e147 C; IR
n
max 3104, 3062, 1609,
20
H N
2
O
10
S
2
1578, 1535, 1502, 1427, 1407, 1372, 1352, 1312, 1300, 1253, 1196,
ꢂ1
1
1
164, 1107, 1088, 1013, 979, 958, 911, 875, 859, 837, 813 cm
NMR (500 MHz, CDCl
7.21 (d, J¼8.7 Hz, 1H), 7.56 (ddd, J¼8.2, 6.7,
1.5 Hz, 1H), 7.68e7.78 (m, 2H), 7.84 (d, J¼8.1 Hz, 1H), 8.26 (d,
; H
4
.2.9. 4-Chloronaphthalen-1-yl 4-nitrobenzenesulfonate (1i). Yield:
3
) d
ꢀ
Conditions C: 88% (2.04 g). Light yellow solid: Mp 187e189
C
13
(
DCM); IR
n
max 3110, 3101, 3068, 1599, 1529, 1503, 1378, 1347, 1313,
J¼8.8 Hz,1H), 8.38 (d, J¼9.0 Hz, 2H), 8.44 (d, J¼9.0 Hz, 2H); C NMR
(125 MHz, CDCl 113.9, 124.2, 127.3, 127.3, 127.8, 128.4, 130.7,
131.0, 141.4, 143.2, 145.8, 151.0, 155.2. HRMS 353.021
SþNa calcd 353.020).
1
6
255, 1181, 1088, 1038, 1019, 946, 846, 803, 763, 740, 701, 678, 664,
24, 592, 542, 458, 416 cm ; H NMR (500 MHz, CDCl ) d 7.21 (d,
3
3
) d
ꢂ1
1
J¼8.3 Hz, 1H), 7.48e7.53 (m, 2H), 7.62 (ddd, J¼8.1, 7.1, 1.3 Hz, 1H),
10 2 5
(C15H N O
7
.82 (d, J¼8.5 Hz, 1H), 8.10 (d, J¼8.8 Hz, 2H), 8.24 (d, J¼8.7 Hz, 1H),
13
8
.34 (d, J¼8.8 Hz, 2H); C NMR (125 MHz, CDCl
24.6,125.1, 125.4, 127.9, 128.0, 128.3, 130.0, 131.5, 131.9, 141.1, 144.2,
51.2. Anal. Calcd for C16 10ClNO S: C, 52.83; H, 2.77; N, 3.85. Found
C, 52.78; H, 2.78; N, 3.79.
3
)
d
118.5, 121.7,
4.3. Typical procedure for the SuzukieMiyaura reaction with
nosylates (Tables 3 and 4)
1
1
H
5
To a solution of aryl nosylate (1 equiv) in dry and degassed THF
(
6 mL/mmol) under inert atmosphere were added successively
boronic acid (2 equiv), Pd(OAc) (2 mol %), 2-
dicyclohexylphosphino-2 ,4 ,6 -triisopropylbiphenyl (XPhos)
4
.2.10. 4-Bromonaphthalen-1-yl 4-nitrobenzenesulfonate (1j). Yield:
2
ꢀ
0
0
0
Conditions C: 96% (944 mg). Light yellow solid: Mp 197
dichloromethane); IR
C
(
n
max 3110, 3095, 3066, 1596, 1528, 1455,
(4 mol %) and potassium phosphate (2.8 equiv). The flask was
ꢀ
1
7
381, 1347, 1312, 1252, 1183, 1089, 1036, 1012, 842, 796, 759, 738,
sealed and the mixture was stirred at 80 C under inert atmosphere
ꢂ1
1
02, 680, 655, 618, 581, 539, 508, 455, 409 cm
7.15 (d, J¼8.4 Hz, 1H), 7.50 (ddd, J¼8.2, 6.8,
.1 Hz, 1H), 7.62 (ddd, J¼8.4, 6.9, 1.2 Hz, 1H), 7.72 (d, J¼8.2 Hz, 1H),
;
H NMR
until consumption of the starting material. The reaction mixture
(
500 MHz, CDCl
3
)
d
was diluted with ethyl acetate and the suspension was filtered over
Ò
1
Celite . The filtrate was concentrated under reduced pressure and
7
.81 (d, J¼8.5 Hz, 1H), 8.10 (d, J¼8.8 Hz, 2H), 8.21 (d, J¼8.6 Hz, 1H),
the crude residue was purified by chromatography on silica gel
(Cyclohexane/Ethyl Acetate).
13
8
.34 (d, J¼8.7 Hz, 2H); C NMR (125 MHz, CDCl
22.1,124.6,127.8, 128.0,128.0,128.6,129.1, 130.0,133.2,141.1,145.0,
51.2. Anal. Calcd for C16 10BrNO S: C, 47.08; H, 2.47; N, 3.43. Found
C, 47.05; H, 2.47; N, 3.45.
3
)
d
118.9, 121.8,
1
1
0
1
H
5
4.3.1. 1-([1,1 -Biphenyl]-4-yl)ethanone (3a). Yield: 93% (92 mg); H
NMR (500 MHz, CDCl 2.64 (s, 3H), 7.38e7.43 (m, 1H), 7.44e7.50
m, 2H), 7.60e7.66 (m, 2H), 7.69 (d, J¼8.3 Hz, 2H), 8.04 (d, J¼8.4 Hz,
3
) d
(
13
4.2.11. Pyridin-3-yl 4-nitrobenzenesulfonate (1k). Yield: Conditions
3
2H); C NMR (125 MHz, CDCl ) d 26.8, 127.3, 127.4, 128.4, 129.0,
A: 99% (291 mg); Conditions B: 70% (3.92 g); Conditions C: 96%
129.1, 135.9, 140.0, 145.9, 197.9. The product exhibits spectroscopic
data identical to those reported in the literature.
ꢀ
23
(
1.96 g). Light brown solid: Mp 112e113 C; IR
n
max 3106, 3054,
3
024, 2870, 2360, 2161, 1979, 1607, 1588, 1573, 1532, 1470, 1425,
ꢂ1
1
0
0
1
(
404, 1378, 1347, 1311, 1300 cm ; H NMR (500 MHz, CDCl
dd, J¼8.4, 4.7 Hz, 1H), 7.49 (ddd, J¼8.4, 2.8, 1.5 Hz, 1H), 8.06 (d,
J¼8.9 Hz, 2H), 8.22 (d, J¼2.7 Hz, 1H), 8.41 (d, J¼8.8 Hz, 2H), 8.56 (dd,
3
)
d
7.35
4.3.2. Methyl 4 -acetyl-[1,1 -biphenyl]-4-carboxylate (3d). Yield:
1
93% (119 mg); H NMR (500 MHz, CDCl
3
) d 2.65 (s, 3H), 3.95 (s, 3H),
7.69 (d, J¼8.4 Hz, 2H), 7.72 (d, J¼8.4 Hz, 2H), 8.05 (d, J¼8.3 Hz, 2H),
13
13
J¼4.7, 1.3 Hz, 1H); C NMR (125 MHz, CDCl
30.1, 140.4, 143.7, 146.2, 149.0, 151.3; HRMS 303.003
SþNa calcd 303.005).
3
)
d
124.7, 124.8, 130.0,
8.13 (d, J¼8.3 Hz, 2H); C NMR (125 MHz, CDCl
3
) d 26.9, 52.4, 127.4,
1
127.6, 129.1, 129.9, 130.4, 136.6, 144.3, 144.6, 166.9, 197.8. The
product exhibits spectroscopic data identical to those reported in
(
11 8 2 5
C H N O
2
4
the literature.
4
.2.12. Pyridin-2-yl 4-nitrobenzenesulfonate (1l). Yield: Conditions
0
1
0
A: 65% (89 mg); Conditions B: 57% (190 mg); Conditions C: 58%
4.3.3. 1-(4 -Methoxy-[1,1 -biphenyl]-4-yl)ethanone (3e). Yield: 98%
ꢀ
(
223 mg). Light yellow crystalline solid: Mp 84e86 C; IR
n
max
(111 mg); H NMR (500 MHz, CDCl
3
) d 2.63 (s, 3H), 3.88 (s, 3H), 7.0
3115, 1610, 1593, 1567, 1532, 1463, 1428, 1403, 1375, 1362, 1348,
(d, J¼8.7 Hz, 2H), 7.58 (d, J¼8.6 Hz, 2H), 7.65 (d, J¼8.3 Hz, 2H), 8.01

A. Dikova et al. / Tetrahedron 72 (2016) 1960e1968
1967
(
1
d, J¼8.2 Hz, 2H); 13C NMR (125 MHz, CDCl
3
)
d
26.8, 55.5, 114.5,
exhibits spectroscopic data identical to those reported in the
literature.
2
9
26.8, 128.5, 129.1, 132.4, 135.4, 145.5, 160.0, 197.9. The product
exhibits spectroscopic data identical to those reported in the
literature.24
4.3.12. 2-Phenylpyridine (3p). Yield: 48% (38 mg). The title com-
pound was prepared according to the procedure described for
heteroaromatic tosylates. To a solution of aryl nosylate (143 mg,
0.51 mmol) in degassed n-butanol (3 mL) under inert atmosphere
were added successively boronic acid (124 mg, 1.02 mmol),
0
1
0
30
4
(
(
1
8
.3.4. 1-(2 -Methoxy-[1,1 -biphenyl]-4-yl)ethanone (3f). Yield: 95%
109 mg); H NMR (500 MHz, CDCl
3
)
d
2.64 (s, 3H), 3.83 (s, 3H), 7.02
d, J¼8.1 Hz, 1H), 7.06 (ddd, J¼7.5, 7.5, 0.7 Hz, 1H), 7.34 (dd, J¼7.6,
.8 Hz, 1H), 7.38 (ddd, J¼7.9, 7.9, 1.8 Hz, 1H), 7.65 (d, J¼8.3 Hz, 2H),
2
Pd(OAc) (2.5 mg, 0.011 mmol), XPhos (10 mg, 0.022 mmol). After
13
.01 (d, J¼8.3 Hz, 2H); C NMR (125 MHz, CDCl
3
)
d
26.8, 55.6, 111.4,
15 min of stirring, degassed water (0.7 mL) and sodium hydroxide
(35 mg, 0.867 mmol) were added. The reaction mixture was stirred
at room temperature for 18 h. The reaction mixture was then di-
luted with ethyl acetate and the suspension was filtered over silica
gel pad. The filtrate was concentrated under reduced pressure and
1
21.0, 128.2, 129.5, 129.6, 129.8, 130.8, 135.5, 143.7, 156.5, 198.0. The
product exhibits spectroscopic data identical to those reported in
the literature.25
4
.3.5. (E)-1-(4-styrylphenyl)ethan-1-one (3h). Yield: 49% (55 mg);
the crude residue was chromatographed on silica gel (Cyclohexane/
1
1
H NMR (500 MHz, CDCl
3
)
d
2.61 (s, 3H), 7.13 (d, J¼16.4 Hz, 1H), 7.23
Ethyl Acetate: 9/1). H NMR (300 MHz, CDCl
3
)
d
7.18e7.29 (m, 1H),
(
2
d, J¼16.4 Hz, 1H), 7.31 (dd, J¼7.5, 7.2 Hz, 1H), 7.39 (dd, J¼7.6, 7.2 Hz,
7.40e7.54 (m, 3H), 7.73e7.78 (m, 2H), 7.98e8.05 (m, 2H), 8.72 (ddd,
1
3
H), 7.54 (d, J¼7.6 Hz, 2H), 7.59 (d, J¼8.4 Hz, 2H), 7.96 (d, J¼8.4 Hz,
J¼4.7, 1.4, 1.4 Hz, 1H); C NMR (75 MHz, CDCl
3
) d 120.7, 122.2, 127.0,
13
2
3
H); C NMR (125 MHz, CDCl ) d 26.7, 126.6, 126.9, 127.5, 128.4,
128.8, 129.1, 136.9, 139.5, 149.8, 157.6. The product exhibits spec-
troscopic data identical to those reported in the literature.
31
128.9, 129.0, 131.6, 136.0, 136.8, 142.1, 197.6. The product exhibits
2
6
spectroscopic data identical to those reported in the literature.
4
.3.13. 2-Phenylquinoline (3q). Yield: 98% (39 mg); 1H NMR
.3.6. 1,1 -Biphenyl (3i). Yield: 61% (47 mg); 1H NMR (500 MHz,
0
(500 MHz, CDCl 7.45e7.49 (m, 1H), 7.51e7.57 (m, 3H), 7.74 (ddd,
4
3
) d
CDCl
3
)
d
7.40 (dd, J¼7.8, 7.4 Hz, 2H), 7.50 (dd, J¼7.8, 7.4 Hz, 4H), 7.66
J¼8.5, 6.9, 1.5 Hz, 1H), 7.84 (dd, J¼8.1, 1.2 Hz, 1H), 7.89 (d, J¼8.5 Hz,
13
13
(
1
d, J¼7.8 Hz, 4H); C NMR (125 MHz, CDCl
3
)
d
127.3, 127.4, 128.9,
1H), 8.14e8.21 (m, 3H), 8.23 (d, J¼8.5 Hz, 1H); C NMR (125 MHz,
41.3. The product exhibits spectrocopic data identical to those
3
CDCl ) d 119.2, 126.4, 127.3, 127.6, 127.7, 129.0, 129.5, 129.8, 129.9,
27
reported in the literature.
136.9, 139.8, 148.4, 157.5. The product exhibits spectroscopic data
3
2
identical to those reported in the literature.
.3.7. [1,1 -Biphenyl]-4-carbaldehyde (3j). Yield: 78% (71 mg); 1
0
H
4
NMR (500 MHz, CDCl
.61e7.67 (m, 2H), 7.76 (d, J¼8.2 Hz, 2H), 7.96 (d, J¼8.3 Hz, 2H),
0.06 (s, 1H); 13C NMR (125 MHz, CDCl
127.5, 127.8, 128.6, 129.2,
30.4, 135.3, 139.8, 147.3, 192.1. The product exhibits spectroscopic
3
) d 7.39e7.45 (m, 1H), 7.46e7.52 (m, 2H),
4.3.14. 2-(Benzo[d][1,3]dioxol-5-yl)quinolone (dubamine) (3r). Yield:
79% (64 mg); H NMR (500 MHz, CDCl ) d (ppm) 6.05 (s, 2H), 6.95 (d,
3
1
7
1
1
3
)
d
J¼8.1 Hz, 1H), 7.5 (ddd, J¼8.0, 7.1, 1.2 Hz, 1H), 7.67 (dd, J¼8.1, 1.8 Hz,
1H), 7.71 (ddd, J¼8.6, 7.1 and 1.2 Hz, 1H), 7.75 (d, J¼1.8 Hz,1H), 7.8 (d,
J¼8.6 Hz, 1H), 7.81 (dd, J¼8.1, 1.2 Hz, 1H), 8.13 (d, J¼8.6 Hz, 1H), 8.18
2
3
data identical to those reported in the literature.
1
3
(
d, J¼8.6 Hz, 1H); C NMR (125 MHz, CDCl
3
) d (ppm) 101.6, 108.2,
4
.3.8. 2-Phenylnaphthalene (3k). Yield: 98% (101 mg); 1H NMR
108.7, 118.8, 122.0, 126.3, 127.2, 127.6, 129.8, 129.9, 134.4, 136.9, 148.4,
148.6, 149.0, 156.9. The product exhibits spectroscopic data identical
to those reported in the literature.
(
(
500 MHz, CDCl 7.40e7.48 (m, 1H), 7.50e7.60 (m, 4H), 7.74e7.88
m, 3H), 7.89e8.01 (m, 3H), 8.11 (br s, 1H); C NMR (125 MHz,
125.7, 125.9, 126.0, 126.4, 127.5, 127.5, 127.8, 128.3, 128.5,
29.0, 132.7, 133.8, 138.6, 141.2. The product exhibits spectroscopic
3
) d
13
19
3
CDCl ) d
1
Acknowledgements
2
8
data identical to those reported in the literature.
We gratefully acknowledge the CNRS and the French Agency of
Research (Grant ANR-09-BLAN-0329 CADISCOM). AD thanks the
French Ministry of Research for a PhD fellowship. NPC thanks the
French Agency of Research for a PhD fellowship.
4
.3.9. 1-Phenylnaphthalene (3l). Yield: 91% (93 mg); 1H NMR
(
500 MHz, CDCl 7.47e7.53 (m, 3H), 7.54e7.63 (m, 6H), 7.94 (d,
J¼8.2 Hz, 1H), 7.97e8.03 (m, 2H); C NMR (125 MHz, CDCl
125.5, 125.9, 126.1, 127.1, 127.3, 127.8, 128.4, 130.2, 131.7, 133.9,
3
) d
13
3
)
d
1
40.4, 140.9. The product exhibits spectroscopic data identical to
Supplementary data
2
3
those reported in the literature.
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2016.02.061.
4
.3.10. 4-Phenylnaphthalen-1-yl 4-nitrobenzenesulfonate (3m). Yield:
72% (149 mg) from 1i; 71% (145 mg) from 1j; Light yellow solid: Mp
ꢀ
125 C (ether); IR nmax 3106, 3067, 2924, 2855,1608,1595,1533,1459,
References and notes
1386,1349,1313,1216,1190, 1090,1036,1013, 941, 844, 810, 769, 742,
ꢂ1
1
7
04 cm ; H NMR (500 MHz, CDCl
3
)
d
7.28 (d, J¼7.7 Hz, 1H), 7.34 (d,
1. (a) de Meijere, A.; Diederich, F. Metal-catalyzed Cross-coupling Reactions, 2nd
J¼7.7 Hz, 1H), 7.41e7.53 (m, 7H), 7.84e7.92 (m, 2H), 8.17 (d, J¼8.8 Hz,
ed.; Wiley-VCH: New York, 2004; (b) Tsuji, J. Palladium Reagents and Catalysts:
New Perspectives for the 21st Century; John Wiley & Sons Ltd: Chichester, UK,
13
2
1
1
H), 8.37 (d, J¼8.8 Hz, 2H); C NMR (125 MHz, CDCl
24.6, 126.2, 126.6, 127.1, 127.1, 127.2, 127.9, 128.6, 130.0, 130.1, 133.1,
39.6, 140.5, 141.6, 144.8, 151.1; HRMS 428.0578 (C22
SþNa
calcd 428.0563).
3
) d 117.9, 121.5,
2004; (c) Negishi, E.-I. Handbook of Organopalladium Chemistry for Organic
Synthesis; Wiley-Interscience: New York, 2002.
H15NO
5
2
. (a) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437e3440;
(b) Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866e867.
. For reviews, see (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457e2483;
3
(
b) Suzuki, A. J. Organomet. Chem. 1999, 576, 147e168; (c) Miyaura, N. J.
4
.3.11. 1-(4-Methoxyphenyl)-4-phenylnaphthalene (3n). Yield: 98%
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1
(
93 mg); H NMR (500 MHz, CDCl
3
)
d
3.93 (s, 3H), 7.09 (d, J¼8.5 Hz,
13
2
H), 7.42e7.60 (m, 11H), 7.97e8.07 (m, 2H); C NMR (125 MHz,
55.5, 113.9, 125.9, 125.9, 126.5, 126.5, 126.6, 126.6, 127.3,
30.3,131.3,132.1,132.2,133.3,139.6,139.6,141.0,159.1. The product
3
CDCl ) d
1

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