Nickel-catalyzed C(sp2)-C(sp2) cross coupling reactions of sulfur-functionalities and Grignard reagents

Article abstract of DOI:10.1007/s10562-013-0979-5

In the present study, the nickel-catalyzed carbon carbon bond formation of a range of sulfur containing substrates with Grignard reagents via desulfurization has been explored. After investigation of different reaction parameters with a well-defined nickel complex an excellent and easy-accessible pre-catalyst was found. The obtained system was capable to convert a broad scope of substrates under mild reaction conditions. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-013-0979-5

Catal Lett (2013) 143:424–431
DOI 10.1007/s10562-013-0979-5
Nickel-catalyzed C(sp2)–C(sp2) Cross Coupling Reactions
of Sulfur-Functionalities and Grignard Reagents
•
Chika I. Someya Maik Weidauer
•
Stephan Enthaler
Received: 28 December 2012 / Accepted: 18 February 2013 / Published online: 12 March 2013
Ó Springer Science+Business Media New York 2013
Abstract In the present study, the nickel-catalyzed car-
bon carbon bond formation of a range of sulfur containing
substrates with Grignard reagents via desulfurization has
been explored. After investigation of different reaction
parameters with a well-defined nickel complex an excellent
and easy-accessible pre-catalyst was found. The obtained
system was capable to convert a broad scope of substrates
under mild reaction conditions.
can be a useful tool [7–10]. In 1979 the nickel based cross-
coupling of thioethers or thiols and Grignard reagents have
been reported by Wenkert and Takei et al. applying
[NiCl2(PPh3)2] as pre-catalyst [11–16]. Afterwards the
methodology was advanced for instance to the transfor-
mation of sulfoxides, sulfones, sulfoximines, sulfonium
salts or thiol esters with Grignard or organometallic
reagents [7–10, 17–46]. More recently, the group of Kno-
chel demonstrated the value of the concept in the cross
coupling reactions of various thio derivatives and func-
tionalized aryl-, heteroaryl-, alkyl-, and benzylic zinc
reagents [47–51]. Recently we have demonstrated the
usefulness of complexes 1 in nickel-catalyzed C–C cross
coupling reactions of organic halides with organometallic
zinc reagents (Scheme 1) [52–54]. Moreover, excellent
reactivity was observed in the hydrodehalogenation of aryl
and alkyl halides and in the hydrodecyanation of aryl
cyanides applying tert-butylmagnesium chloride as reagent
[55, 56]. On the other hand complexes 1 allow the hyd-
rodesulfurization of organic compounds by cleavage of
carbon sulfur bonds [55, 56]. In this regard, we report
herein our studies on the nickel-catalyzed carbon carbon
bond formations via desulfurization reactions.
Keywords Catalysis ꢀ Cross coupling ꢀ Nickel ꢀ Sulfur
compounds ꢀ Grignard reagents
1 Introduction
During the last decades nickel-catalyzed carbon–carbon
bond formations have been extensively studied and now-
adays it is a methodology of choice with a broad applica-
bility in the synthesis of fine chemicals, pharmaceuticals,
agricultural chemicals and natural products [1, 2]. Com-
monly, for creating a carbon–carbon bond organic halides
were reacted with organometallic reagents in the presence
of nickel catalysts [3–6]. Contrary to the well explored
halides as leaving group the application of other functions
(e.g., C–OC, C–CN, C–N, C–S) has been less explored.
Interestingly, such functions can be valuable for the crea-
tion of complex molecules since a different reactivity
compared to halides is feasible. In this regard, the con-
version of carbon–sulfur bonds to carbon–carbon bonds
2 Results and Discussion
Initially, the cross coupling of thioanisole (2) with 4-ani-
sylmagnesium bromide (3) in THF was studied as a model
reaction to explore appropriate conditions and to examine
the influence of various reaction parameters (Table 1). As
expected when performing the reaction in the absence of
nickel complexes no product formation was monitored
(Table 1, entry 1). However, when applying 2.5 mol% of
1a 72 % of the cross coupling product 4 was obtained after
C. I. Someya ꢀ M. Weidauer ꢀ S. Enthaler (&)
Cluster of Excellence ‘‘Unifying Concepts in Catalysis’’,
¨
Department of Chemistry, Technische Universitat Berlin,
Straße des 17. Juni 115/C2, 10623 Berlin, Germany
e-mail: stephan.enthaler@tu-berlin.de
123

Cross Coupling Reactions of Sulfur-Functionalities and Grignard Reagents
425
1
: R = Ph, R2 = CF3, R3 = CF3, L = PPh3
favoured. Recently, the group of Miller reported on the
increase of reactivity by addition of LiOtBu to Grignard
reagents [57–60]. Interestingly, the addition of 1.5 equiv.
of LiOtBu to the reaction mixture lead to full conversion
after 1 h, probably by de-aggregation of organomagnesium
clusters or increasing the basicity of the Grignard reagent
(Table 1, entry 6) [61]. Noteworthy, in the absence of the
nickel complex no product formation was observed,
excluding a LiOtBu mediated reaction pathway. In general,
the realized catalyst performance is to some extend
improved in comparison to the earlier system estab-lished by
Wenkert and coworkers, while 10 mol% of [NiCl2(PPh3)2]
resulted in the formation of less than 80 % yield of the
desired products at higher temperature (80 °C) [11–16].
Once the optimized reaction conditions were established
(Table 1, entry 7) the scope and limitations of the nickel-
catalyzed cross coupling of substrates containing thio-
functionalities and Grignard reagents were investigated.
Moreover, the reaction outcome was studied in the presence
and absence of stoichiometric amounts of LiOtBu. First
different para-substituted thioanisoles were reacted with
4-anisylmagnesium bromide (3). An excellent yield was
1a
R1
: R1 = Me, R2 = CF3, R3 = CF3, L = PPh3
1c: R1 = Ph, R2 = CF3, R3 = CF3, L = HyPyPhos
1d: R1 = Ph, R2 = CF3, R3 = CF3, L = (dmap)3
1e: R1 = Me, R2 = CF3, R3 = CF3, L = (dmap)3
1b
O
L
N
Ni
N
O
R2
R3
Scheme 1 Selection of nickel complexes applied in cross coupling
reactions
24 h at 70 °C (Table 1, entry 2). Noteworthy, as side
reaction the homo coupling of 3 and the homo coupling of
2 (\7 %) were observed. The yield of the desired product
was increased to 77 % by increasing the catalyst loading to
5.0 mol % (Table 1, entry 3). Interestingly, the nickel
catalyst demonstrated activity at room temperature
(Table 1, entry 5). Moreover, the influence of the ligand
structure of the nickel complex was studied (Table 1,
entries 10–15). A better performance was observed for
square planar phosphane complexes (1a–1c), while for the
octahedral 4-dimethylaminopyridine complexes (1d–1e) a
reduced yield was monitored. In more detail, within the
phosphane systems the triphenylphosphane ligand was
Table 1 Nickel-catalyzed cross coupling of thioanisole (2) and 4-anisylmagnesium bromide (3) – optimization of the reaction conditions
Entrya
Pre-catalyst [mol%]
T [°C]
T [h]
Sel. [%]b
Yield [%]c
1
–
70
70
70
70
r.t.
70
70
70
70
70
70
70
70
70
70
24
24
24
24
24
24
24
1
\1
95
\1
72
2
1a (2.5)
1a (5.0)
1a (5.0)
1a (5.0)
1a (5.0)
1a (5.0)
1a (5.0)
–
3
94
77
81d
4
[99
95
5
63
6
[99
93
[99e
87f
[99e
\1e
73
[99e
[99e
72
7
8
[99
\1
95
9
1
10
11
12
13
14
15
a
1b (5.0)
1b (5.0)
1b (5.0)
1c (5.0)
1d (5.0)
1e (5.0)
24
24
1
[99
[99
99
24
24
24
96
67
[99
39
Reaction conditions: 2 (0.2–0.6 mmol), pre-catalyst 1 (2.5–5 mol%), 3 (1.5 equiv., 1.0 M in THF), THF (2.0 mL), r.t-70 °C, 1-24 h
Selectivity. As side product 1,10-biphenyl was observed
b
c
d
e
f
Determined by GC–MS applying n-dodecane as internal standard
2.0 equiv. 3
1.5 equiv. LiOtBu
(5.0 mmol), pre-catalyst 1 (5 mol %), 3 (1.5 equiv., 1.0 M in THF), THF (7.5 mL), 1.5 equiv. LiOtBu, isolated yield 66 %
123

426
C. I. Someya et al.
Table 2 Nickel-catalyzed cross coupling of thio-functionalities and 4-anisylmagnesium bromide (3)—scope and limitations
Entrya Substrate
Product
Sel. [%]b
>99 (94)
Yield [%]c
SMe
OMe
1
4: >99 (77)
2
OMe
SMe
2
>99 (>99)
<1 (<1)
5a: 96 (62)
5
OMe
SMe
3
6a: <1 (<1)d
Br
6
Br
SMe
OMe
4
5
6
7
8
9
NC
7
>99 (<1)
>99 (>99)
>99 (>99)
92 (94)
97
7a: 21 (<1)e
4: 43 (51)
4: 84 (85)f
4: 66 (73)
4: 69g
NC
OMe
S
S
Cl
8
8
OMe
Cl
OMe
OMe
S
9
9
S
S
OMe
>99 (>99)
>99 (>99)
10a: 30 (36)
10a:70 (37)f
MeO
10
10
S
10
OMe
MeO
OMe
O
S
11
12
13
>99 (>99)
>99 (>99)
>99
4: 50 (35)
4: 78 (81)
4: 42g
11
OMe
OMe
O
S
12
12
O
S
123

Cross Coupling Reactions of Sulfur-Functionalities and Grignard Reagents
427
Table 2 continued
Entrya Substrate
Product
Sel. [%]b
Yield [%]c
OMe
OMe
O
S
14
>99 (>99)
5a: 70 (65)
13
13
O
S
15
>99
5a: 50g
OMe
O
S
16
<1 (70)
>99 (73)
14a: <1 (21)
4: 80 (73)
14
O
O
O
O
OMe
S
S
17
18
15
OMe
>99
4: 68g
15
a
Reaction conditions: substrate (0.3 mmol), pre-catalyst 1a (5 mol%), Grignard reagent 3 (1.5 equiv., 1.0 M in THF), LiOtBu (1.5 equiv.),
THF (2.0 mL), 70 °C, 24 h
b
In brackets the selectivity for the reaction in the absence of LiOtBu is given. As side product corresponding biphenyls were observed
c
d
e
f
1
Determined by GC-MS and H NMR. In brackets the yield for the reaction in the absence of LiOtBu is given
47 % (22 %) cross coupling at the C-Br was observed
28 % cross coupling at the C-CN was observed for the LiOtBu free system
2.5 equiv. 3 and LiOtBu
g
2.5 equiv. 3, the isolated yield corresponds to the conversion of both substituents on the sulfur
observed for the methyl substituent in para-position, while in
case of bromo- and cyano-substitution the cross coupling
appeared at the bromo- or cyano-position (Table 2, entries
2–4). On the other hand 2-chloroethyl-phenylsulfide (8) gave
the coupling product 4, while a cross coupling (sp2–sp3) at
the chloro-substituent was not observed (Table 2, entries 5
and 6). The reaction outcome was increased by addition of
2.5 equiv. of the Grignard reagent. Next, thioethers con-
taining two sp2-carbons connected to the sulfur were tested
(Table 2, entries 7–10). Diphenylsulfone (9) was converted
in 73 % to the desired product. In contrast, for dibenzo-
thiophene (10) as major product the 2,20-disubstituted
biphenyl 10a was observed. Furthermore, the reaction with
2.5 equiv. of the Grignard reagents 3 and LiOtBu gave higher
yield of the coupling product 10a. In addition, sulfoxides
with aromatic substituents were reacted with the Grignard
reagent 3 in the presence of 1a (Table 2, entries 10–15).
Good yields of the desired product were achieved, while for
the benzyl sulfoxide (14) only a moderate amount of product
was formed (Table 2, entry 16). Moreover, a comparable
yield to phenyl sulfoxide (12) was observed for the conver-
sion of the sulfone 15 (Table 2, entry 17 and 18). In addition,
for symmetrical substrates (e.g., 9, 12, 13, and 15) 2.5
equivalents of the Grignard reagent 3 were used (Table 2,
entries 8, 13, 15 and 18). Interestingly, for substrates 9 and 15
both substituents were converted to the corresponding biaryl
product.
In order to study the influence of the nucleophiles dif-
ferent Grignard reagents were reacted with thioanisole (2)
(Table 3). Excellent yield was observed for the reaction
with p-tolylmagnesium bromide (Table 3, entry 2). Fur-
thermore, a variety of Grignard reagents were pre-gener-
ated by direct Mg insertion to the bromide in the presence
of LiCl [62–69]. The cross coupling reaction of each
Grignard reagents and thioanisole (2) in the presence of
5 mol% of pre-catalyst 1a gave the desired coupling
products in good to excellent yields (Table 3, entries 3–8).
Moreover, alkyl Grignard reagents were examined, how-
ever resulting in no formation of product.
Moreover, for studying the abilities of the thioether
function in comparison to other leaving groups an equi-
molar mixture of 4-iodoanisole (23), 4-bromoanisole (24),
4-chloroanisole (25), 4-fluoroanisole (26), and 4-meth-
oxythioanisole (27) were reacted with stepwise increasing
amounts of p-tolylmagnesium bromide (16, 1–3 equiv.)
(Figure 1). After addition of the first equivalent of 16 as
expected a decrease of the concentration of 4-iodoanisole
(23) was noticed. Increasing the amount of equivalents of
Grignard reagent the conversion of the 4-bromoanisole
(24) and 4-methoxythioanisole (27) was observed, while
123

428
C. I. Someya et al.
Table 3 Nickel-catalyzed cross coupling of thioanisole (2) and Grignard reagents—scope and limitations
Entry Substrate
Product
Sel. [%]a
94 (>99)
Yield [%]b
OMe
MgBr
1
4: 77 (>99)c
MeO
3
MgBr
2
3
4
93 (>99)
>99
16a: 62 (78)c
4: 76d
16
OMe
tBu
MgBr LiCl
MeO
tBu
17
MgBr LiCl
>99
18a: 73d
18
MgBr LiCl
MgBr LiCl
N
5
>99
19a: 76d
N
19
20
6
7
>99
>99
20a: 64d
21a: 70d
MgBr LiCl
21
tBu
tBu
MgBr LiCl
8
>99
22a: 95d
tBu
tBu
22
a
b
c
1
Determined by GC-MS and H NMR. In brackets the yield for the reaction in the presence of 1.5 equiv. LiOtBu is given
In brackets theselectivity for the reaction in the absence of LiOtBu is given. As side product corresponding biphenyls were observed
Reaction conditions: substrate (1.0 mmol), pre-catalyst 1a (5 mol%), Grignard reagent (1.5 equiv., 1.0–2.0 M in THF), THF (2.0 mL), 70 °C,
24 h
d
Grignard reagents were pre-generated, see Ref. [62–69]. Reaction condition: substrate (0.7 mmol), aryl bromide (1.0 mmol), Mg (1.1 mmol),
LiCl (1.0 mmol), pre-catalyst 1a (5 mol%), THF (5 mL), 70°C, 24 h
4-chloroanisole (25) and 4-fluoroanisole (26) were almost
unreacted. In more detail, the found reactivity is in line with
the bond dissociation energy of each bonds (Ar–I: 64 kcal
mol-1, Ar–Br: 79 kcal mol-1, Ar–Cl: 95 kcal mol-1, Ar–F:
124 kcal mol-1, Ar–SMe: 77 kcal mol-1) [70].
form the paramagnetic complex 1a-1 [52–54]. The com-
plex 1a-1 reacts with the Grignard reagents to create
complex 1a-2 or 1a-3 containing a 4-membered ring sys-
tem [61]. The organic sulfide approaches the coordination
sphere of the nickel and mediates a single electron transfer
(SET) to oxidize the complex and produce a radical. The
one-electron oxidized complex can be on the one hand
oxidized at the metal center (1a-4 or 1a-5) or on the other
hand the electron can be stored in the ligand (non-inocent
ligand: 1a-6 or 1a-7). Subsequently, RSMgX is eliminated
and the radical recombines with the nickel species to form
Based on the preliminary results we propose a reaction
mechanism as presented in Scheme 2 [52–56]. Initially the
triphenylphosphane ligand dissociates from complex 1a to
create an open coordination site. In an earlier NMR study
the dissociation was followed by 31P NMR and free coor-
dination sites were occupied by the reaction solvent THF to
123

Cross Coupling Reactions of Sulfur-Functionalities and Grignard Reagents
429
I
Br
Cl
MeO
MeO
F
MeO
SMe
5.0 mol% 1a
1-3 equiv. 16
23
24
25
THF, 70°C, 24-72h
MeO
n-dodecane
5a
MeO
MeO
27
26
100
80
60
40
20
Yield [%]
1
0
2
16 [equiv.]
25
26
3
24
27
23
Substrate
Fig. 1 Reactivity study. [Reaction conditions: 23, 24, 25, 26, and 27 (each 1.0 mmol), pre-catalyst 1a (5 mol%, 0.05 mmol), 16 (every 24 h 1.0
equiv., 1.0 M in THF), THF (10 mL), 70 °C.]
X
Mg
Ph
Ph
O
O
Ar
Ar
N
Mg
X
N
Ni
Ni
N
N
O
O
F3C
CF3
F3C
CF3
R-SR
1a-2 [Ni(II)]
1a-3 [Ni(II)]
Ar MgX
R
R
O
Ph
Ph
X
Mg
Ph
N
Ph
N
SR
O
O
PPh3
(thf)x
O
Ar
N
N
xTHF
PPh3
Ni
Ni
Ar
Mg
X
Ni
Ni
N
O
N
O
SR
CF3
N
N
O
O
F3
C
CF3
F3
C
CF3
F3
C
F3
C
CF3
1a [Ni(II)]
1a-1 [Ni(II)]
RS Mg X
Ph
1a-4 [Ni(IV)]
1a-5 [Ni(IV)]
O
R
Ar
N
C
Ni
or
N
O
Ar
R
F3
CF3
xTHF
R
R
X
Ph
Ph
SR
Ar
1a-8 [Ni(IV)]
Mg
O
O
Ar
N
N
Mg
X
Ni
Ni
SR
CF3
1a-7 [Ni(III)]
N
N
O
O
F3C
F3C
CF3
1a-6 [Ni(III)]
Scheme 2 Proposed catalytic cycle for the nickel-catalyzed cross-coupling reaction of aryl Grignard reagents and organic sulfur compounds
123

430
C. I. Someya et al.
1
the intermediate 1a-8. Finally, an elimination of Ar–R
occurs to regenerate complex 1a-1.
3.3.2. 4-Methoxy-40-methyl-1,10-biphenyl [72] (5a): H
NMR (CDCl3, 200 MHz) d = 7.54–7.44 (m, 4H), 7.24–7.20
(m, 2H), 6.98–6.94 (m, 2H), 3.82 (s, 3H), 2.38 (s, 3H) ppm.
13C{1H} NMR (CDCl3, 50 MHz) d = 158.8, 138.0, 136.4,
133.8, 129.5 (2C), 128.0 (2C), 126.6 (2C), 114.3 (2C), 55.4,
21.1 ppm. MS (EI) m/z = 199 (15), 198 (100, M?), 183 (50),
155 (32), 153 (11), 152 (11), 128 (12), 115 (11), 40 (16).
3.3.3. 4-Cyano-1,10-biphenyl [73] (7a): MS (EI) m/z =
209 (25, M?), 166 (11), 40 (100).
In summary, we have set up a nickel-catalyzed carbon–
carbon cross coupling protocol applying sulfur containing
substrates as electrophiles and Grignard reagents as
nucleophiles. With the well-defined nickel complex 1a a
variety of thioethers, sulfoxides and sulfones were con-
verted to the desired products.
1
3.3.4. 2,20-Bis(p-anisyl)-1,10-biphenyl (10a): H NMR
3 Experimental Section
(CDCl3, 200 MHz) d = 7.53–6.96 (m, 14H), 3.75 (s, 3H)
ppm. 13C{1H} NMR (CDCl3, 50 MHz) d = 158.1 (2C),
140.7 (2C), 133.8 (2C), 131.7 (2C), 130.3 (3C), 130.0 (2C),
127.5 (2C), 126.9 (2C), 113.0 (3C), 55.3 (2C) ppm. MS
(EI) m/z = 367 (28), 366 (100, M?), 215 (12), 40 (50).
3.3.5. 1-Benzyl-4-methoxybenzene [74] (14a): MS (EI)
m/z = 198 (27, M?), 197 (10), 167 (11), 40 (100).
3.3.6. 4-Methyl-1,10-biphenyl [75] (16a): 1H NMR
(CDCl3, 200 MHz) d = 7.71–7.33 (m, 8H), 2.50 (s, 6H)
ppm. 13C{1H} NMR (CDCl3, 50 MHz) d = 141.3, 138.4,
136.8, 137.1, 129.6 (2C), 128.8 (2C), 127.2 (2C), 127.1
(2C), 21.2 ppm. MS (EI) m/z = 168 (51, M?), 167 (33),
165 (13), 153 (10), 152 (13), 40 (100).
3.1. General: All manipulations with oxygen- and moisture-
sensitive compounds were performed under dinitrogen using
standard Schlenk techniques. 1H and 13C were recorded on a
Bruker AFM 200 spectrometer (1H: 200.13 MHz; 13C:
50.32 MHz) using the proton signals of the deuterated sol-
vents as reference. GC–MS measurements were carried out
ona ShimadzuGC-2010 gas chromatograph (30 m Rxi-5 ms
column) linked with a Shimadzu GCMA-QP 2010 Plus mass
spectrometer.
3.2. General procedure for the cross coupling reaction: A
Schlenk flask was charged with an appropriate amount of
complex 1a (0.02 mmol, 5.0 mol%) and the corresponding
thioether (0.3 mmol). The flask was cycled with nitrogen and
vacuum. Afterwards THF (2.0 mL) and a THF solution of the
corresponding Grignard reagent (1.5 equiv., 1.0 M in THF)
were added. The flask was sealed and heated at 70 °C for 24 h
or stirred at room temperature. After that time, the mixture was
cooled, and dichloromethane and an aqueous NH4Cl solution
were added. The aqueous phase was extracted with dichloro-
methane and dried over Na2SO4. n-Dodecane (internal stan-
dard) was added and an aliquote was taken and for GC–MS
analysis. The solvent was removed and the residue was purified
by column chromatography (eluent: toluene). The products
were confirmed by GC–MS and NMR analysis. The analytical
properties of the products are in agreement with literature data.
3.3. General procedure for the preparation of Grignard
reagents via direct Mg insertion in the presence of LiCl: A
25 mL Schlenk tube flushed with nitrogen was charged
with LiCl (1 mmol), Mg (1.1 mmol) and of THF (1.5 mL)
was added under nitrogen. To the slurry solution of aryl
bromide in THF (1 mmol was dissolved in 2.0 mL) was
added and stirred vigorously. The reaction mixture was
stirred over night at room temperature.
1
3.3.7. 4-(tert-Butyl)-1,10-biphenyl [76] (18a): H NMR
(CDCl3, 200 MHz) d = 7.60–7.28 (m, 9H), 1.35 (s, 9H)
ppm. 13C{1H} NMR (CDCl3, 50 MHz) d = 150.4, 141.2,
138.3, 128.8, 127.1, 126.9, 126.8, 125.8, 34.6, 31.5 ppm.
MS (EI) m/z = 195 (100), 40 (67), 210 (37, M?), 167 (30),
41 (20), 84 (17), 196 (17), 152 (13), 155 (11), 165 (11).
3.3.8. 4-(N,N-Dimethylamino)-1,10-biphenyl [77] (19a):
1H NMR (CDCl3, 200 MHz) d = 7.65–6.84 (m, 9H), 3.03
(s, 6H) ppm.13C{1H} NMR (CDCl3, 50 MHz) d = 150.4,
141.2, 138.3, 128.8 (2C), 127.1 (2C), 126.9 (2C), 126.8
(2C), 125.8 (2C), 34.6, 31.5 (2C) ppm. MS (EI) m/z = 197
(100, M?), 196 (73), 40 (53), 152 (21), 98 (19), 181 (17),
198 (16), 153 (12), 90 (12).
3.3.8. 2-Phenylnaphthalene [76] (20a): 1H NMR (CDCl3,
200 MHz) d = 8.03–7.33 (m, 12H) ppm. 13C{1H} NMR
(CDCl3, 50 MHz) d = 141.3, 138.6, 133.9, 132.8, 129.0,
128.4, 128.3, 127.6, 127.5, 127.4, 126.4, 126.0, 125.9, 125.7
ppm. MS (EI) m/z = 204 (100, M?), 202 (49), 40 (43), 203
(38), 101 (30), 205 (23), 102 (16), 89 (14), 76 (12), 88 (12).
3.3.9. 2,4,6-Trimethyl-1,10-biphenyl [78] (21a): 1H NMR
(CDCl3, 200 MHz) d = 7.57–7.35 (m, 5H), 7.14 (s, 2H),
7.53 (s, 3H), 2.21 (s, 6H) ppm. 13C{1H} NMR (CDCl3,
50 MHz) d = 141.2, 139.2, 136.6, 136.0, 129.4, 128.4,
128.1, 126.6, 20.9, 20.8 ppm. MS (EI) m/z = 40 (100), 196
(30, M?), 181 (25), 165 (14).
3.3.1. 4-Methoxy-1,10-biphenyl [71] (4): 1H NMR
(CDCl3, 200 MHz) d = 7.68–7.75 (m, 4H), 7.61–7.47 (m,
3H), 7.13 (d, J = 8.7 Hz, 2H), 3.93 (s, 3H) ppm. 13C{1H}
NMR (CDCl3, 50 MHz) d = 159.2, 140.8, 133.7, 128.8
(2C), 128.1 (2C), 126.6, 126.7 (2C), 114.3 (2C), 55.2 ppm.
MS (EI) m/z = 185 (16), 184 (100, M?), 169 (52), 141
(58), 139 (14), 115 (49), 63 (12), 40 (56).
3.3.10. 3,5-Di-tert-butyl-1,10-biphenyl [79] (22a): 1H
NMR (CDCl3, 200 MHz) d = 7.82–7.41 (m, 8H), 1.59
(s, 18H) ppm. 13C{1H} NMR (CDCl3, 50 MHz) d = 151.2
(2C), 140.9, 142.7, 128.8 (2C), 127.6 (2C),127.1, 121.9
123

Cross Coupling Reactions of Sulfur-Functionalities and Grignard Reagents
431
35. Fuwa H, Nakajima M, Shi J, Takeda Y, Saito T, Sasaki M (2011)
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(2C), 121.5, 35.11 (2C), 31.7 (6C) ppm. MS (EI) m/z = 40
(100), 251 (83), 57 (63), 266 (30, M?), 41 (28), 252 (18).
Acknowledgments Financial support from the Cluster of Excel-
lence ‘‘Unifying Concepts in Catalysis’’ (funded by the Deutsche
Forschungsgemeinschaft and administered by the Technische Uni-
¨
versitat Berlin) is gratefully acknowledged.
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