Hiyama cross-coupling of arenediazonium salts under mild reaction conditions

Article abstract of DOI:10.1021/jo201437j

Palladium acetate [Pd(OAc)₂]-catalyzed Hiyama cross-coupling of arenediazonium salts with organosilanes was found to generate biaryl products in high yields in alcoholic solutions. The simple and efficient protocol does not require any bases, ligands, or air/moisture. The transformation can tolerate either electron-donating or electron-withdrawing functional groups. Theoretical studies show that the transmetalation is the rate-limiting step for the cross-coupling reaction and both acetate and tetrafluoroborate anions may be involved in the direct reaction with the silicon atom.

Full text of DOI:10.1021/jo201437j

Article
pubs.acs.org/joc
Hiyama Cross-Coupling of Arenediazonium Salts under Mild
Reaction Conditions
Kai Cheng,†,§ Chen Wang,† Yiyuan Ding,‡ Qingbao Song,‡ Chenze Qi,*,† and Xian-Man Zhang†
†Institute of Applied Chemistry and Department of Chemistry, University of Shaoxing, Shaoxing, Zhejiang Province 312000, People’s
Republic of China
‡College of Chemical & Materials Science, Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China
§Zhejiang Huangma Chemical Industry Group Co. Ltd., Shangyu, Zhejiang Province 312363, People’s Republic of China
S
* Supporting Information
ABSTRACT: Palladium acetate [Pd(OAc)2]-catalyzed Hiya-
ma cross-coupling of arenediazonium salts with organosilanes
was found to generate biaryl products in high yields in
alcoholic solutions. The simple and efficient protocol does not
require any bases, ligands, or air/moisture. The transformation can tolerate either electron-donating or electron-withdrawing
functional groups. Theoretical studies show that the transmetalation is the rate-limiting step for the cross-coupling reaction and
both acetate and tetrafluoroborate anions may be involved in the direct reaction with the silicon atom.
Arenediazonium salts are both attractive and useful electro-
philes for the palladium-catalyzed chemistry.10 Compared to
other coupling partners such as aryl halides and triflates,
arenediazonium salts have much higher reactivity as well as the
wider availability from inexpensive anilines. Although arenedia-
zonium salts have been used in some palladium-catalyzed
coupling reactions including Mizoroki−Heck,11 Suzuki−
Miyaura,12 and Stille reactions,13 the studies are scarce in the
literature for the palladium catalyzed Hiyama cross-coupling of
arenediazonium salts. As far as we know, the only attempt was
the PdCl2-catalyzed reaction of phenyltrimethoxysilane with
arenediazonium salts, which gave only at 20−48% of the
desired biaryl products.14 In this paper, we report a practical
and efficient protocol for the Pd(OAc)2-catalyzed Hiyama-type
cross-coupling without the need for additional bases and
ligands under mild reaction conditions. The reaction
mechanism has also been examined by theoretical calculations.
INTRODUCTION
■
The importance of palladium catalyzed cross-coupling reactions
for the carbon−carbon chemical bond formation can hardly be
overestimated in synthetic organic chemistry.1 Indeed in the
past several decades, palladium-catalyzed reactions have been
developed into a routine method for the preparation of fine
chemicals, polymers, agrochemicals, and pharmaceutical inter-
mediates in the academic laboratory as well as the large-scale
industrial applications.2 The key step for the cross-coupling is
the transmetalation of the organometallic reagents with
electrophiles such as in Kumada,3 Negishi,4 Stille,5 and Suzuki
coupling reactions.6 However, these catalyzed couplings suffer
many drawbacks for the practical applications. For example, a
large excess of toxic tin reagents are needed for the Stille cross-
coupling, resulting in a large amount of the organotin waste.
For the Suzuki cross-coupling, the highly functionalized
organoboron reagents are difficult to prepare and are also not
easy to purify and handle. Moreover, they frequently lose the
boron functional groups to form the undesirable homocoupling
products.
Recently, the use of silicon-derived compounds as alternative
reagents for the cross-coupling transformations (Hiyama
coupling reaction)7 has attracted much attention due to their
low cost, easy availability, environmentally benign nature, as
well as the tolerance to the different functional groups.8
Although organosilicon reagents have been employed for the
synthesis for a wide variety of applications such as natural
products and biologically active compounds, the highly
complex phosphine ligand and catalyst are expensive and
difficult to prepare and handle together with the difficulty for
the postprocessing. Moreover, activation by base such as
fluoride and hydroxide are essential for the formation of
biaryls.9 Thus, it is still desirable to develop inexpensive and
efficient catalytic methods for the Hiyama cross-coupling
reaction under mild reaction conditions.
RESULTS AND DISCUSSION
■
Pd(II)-Catalyzed Hiyama Cross-Coupling of Arenedia-
zonium Salts. The initial reaction conditions were optimized
using phenyltriethoxysilane and 4-methylbenzenediazonium
tetrafluoroborate salt as the model substrates in methanol
with 5 mol % of PdCl2 at 25 °C for 6 h under air. Only 45%
yield of the desired cross-coupling product was isolated from
the PdCl2-catalyzed reaction (Table 1, entry 1). A slight
improvement was observed for the PdI2-catalyzed reaction
(Table 1, entry 2). No significant improvement of the cross-
coupling yields was achieved for the palladium catalysts
containing phosphine ligands (Table 1, entries 3−5).
Interestingly, the desired cross-coupling product was obtained
in 81% yield from the Pd(OAc)2-catalyzed reaction (Table 1,
Received: July 15, 2011
Published: October 13, 2011
© 2011 American Chemical Society
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a
obtained for phenyltriethoxysilane, phenyltrimethoxysilane, and
dimethoxydiphenylsilane (Table 3, entries 1−3). The methyl,
fluoro, and trifluoromethyl groups seem to have negligible
effects on the cross-coupling (Table 3, entries 4−6). Also, the
heterocyclic derivative (benzofuran-2-yltrimethoxysilane) could
be employed as the electrophile to give 2-(p-tolyl)benzofuran
in a yield of 80% (Table 3, entry 7).
Table 4 summarizes the cross-coupling reactions for a series
of arenediazonium tetrafluoroborate salts with dimethoxydi-
phenylsilane in moderate to good yields. The catalytic system
not only tolerates various functional groups such as NO2, Cl,
Br, and OMe, but the substituents have similar effects on the
cross-coupling yields regardless of their polarity (Table 4,
entries 1−6). In addition, the steric effects of arenediazonium
salts seem to be negligible on the coupling yields (Table 4,
entries 7−10). Most interestingly, the cross-coupling of 4-
bromobenzenediazonium tetrafluoroborate salt with diphenyl-
dimethoxysilane gave exclusively 4-bromobiphenyl in 89% yield
(Table 4, entry 4). The high chemoselectivity is in contrast to
the traditional Hiyama cross-coupling.7
Table 1. Effects of Catalysts on the Cross-Coupling Reaction
b
entry
catalyst
yield (%)
1
2
PdCl2
PdI2
45
54
63
42
40
81
−
3
PdCl2(dppf)
PdCl2 (PPh3)3
Pd(PCy3)2Cl2
Pd(OAc)2
4
5
6
7
RhCl(PPh3)3
[RuCl2(p-cymene)]2
Pd(PPh3)4
8
−
9
29
23
75
10
11
Pd2(dba)3
c
Pd(OAc)2
a
Reaction conditions: phenyltriethoxysilane (0.6 mmol), 4-methyl-
benzenediazonium tetrafluoroborate salt (0.5 mmol), catalyst (5.0 mol
%), CH3OH (2 mL), 25 °C, 6 h. Isolated yields. Using 1.0 mol % of
b
c
Pd(OAc)2 as catalyst.
Primary alcohols are essential for this catalytic trans-
formation, suggesting that they were involved with the
reduction of the oxidative Pd(II) into the reductive Pd(0)
species.1g This conclusion is consistent with no cross-coupling
product in non- or weakly reductive alcohols such as t-BuOH
and i-PrOH. In order to study the effects of alcohol further, we
chose THF which is a completely inert solvent for the cross-
coupling of the model reaction. Addition of the reductive PVA
8000 [poly(vinyl alcohol)] (0.05 mmol) resulted in 24% of the
cross-coupling product (4-methylbiphenyl) after reaction for
0.5 h. Interestingly, the cross-coupling reaction did not stop
even when the PVA was removed from the reaction system by
filtration since the final cross-coupling yield was reached to 65%
after reaction for another 5.5 h.
entry 6). Also, the transition-metal sources were critical for the
cross-coupling reaction (Table 1, entries 7 and 8). Relatively
lower cross-coupling yields were obtained for the zerovalent
palladium catalysts such as Pd(PPh3)4 and Pd2(dba)3 (Table 1,
entries 9 and 10). It is worth noting that a decent yield was still
obtained at 1.0 mol % of the Pd(OAc)2 catalyst loading (Table 1,
entry 11).
Among the solvents tested, the cross-coupling product was
found to be negligible in both nonpolar solvents (such as
ethers, aromatics, and chloromethanes) and polar aprotic
solvents (such as DMF and DMSO) (Table 2, entries 1−9).
a
Table 2. Solvent Effects on the Cross-Coupling Reaction
Mechanism Investigation. The catalytic cycle of the
Hiyama reaction is generally believed to proceed via three steps
(Scheme 1): (1) oxidative insertion of the aryl complex to the
Pd(0) complex to form the aryl-Pd(II) complex; (2) trans-
metalation between the aryl-Pd(II) complex and the arylsilane
to generate the (aryl)(aryl)palladium(II) species; (3) reductive
elimination of the (aryl)(aryl)palladium(II) species to produce
the biaryl product with the regeneration of Pd(0) complex.
Hiyama et al. have found that the acceleration of the trans-
metalation was caused by fluoride anion for the Pd-catalyzed
cross-coupling reaction between vinyl iodide and vinylsilane.15
The Hammett correlation slope was found to be positive for
the Pd-catalyzed cross-coupling reaction of allyl carbonate with
arylsiloxane, suggesting that the rate-determining step should
be involved with a negatively charged transition state, which
could be either the transmetalation or reductive elimination.16
Although fluoride anion (e.g., TBAF) was required to facilitate
these reactions, there are no additional bases (e.g., fluoride
anion) and phosphine ligands in our catalytic system. Thus,
we propose that the tetrafluoroborate anion may react as the
nucleophilic reagent to attack the Si atom. In order to test this
hypothesis, we have carried out a systematic study of this
reaction system using the density functional theory (DFT)
calculation.17
b
b
yield
yield
entry
solvent
THF
(%)
entry
solvent
methanol
(%)
1
2
3
4
5
6
7
8
9
−
−
−
−
−
−
−
−
−
10
11
12
13
14
15
16
17
18
81
66
58
53
44
−
−
−
−
1,4-dioxane
DME
ethanol
propan-1-ol
butan-1-ol
hexane
toluene
CH2Cl2
CCl4
pentan-1-ol
propan-2-ol
cyclohexanol
pentan-3-ol
tert-butyl alcohol
DMF
DMSO
a
Reaction conditions: phenyltriethoxysilane (0.6 mmol), 4-methylben-
zenediazonium tetrafluoroborate salt (0.5 mmol), Pd(OAc)2 (5 mol %),
b
solvent (2 mL), 25 °C, 6 h. Isolated yields.
Similarly, no cross-coupling products were obtained in
secondary or tertiary alcohols (Table 2, entries 15−18).
However, decent cross-coupling yields were obtained when
carried out in the primary alcoholic solvents (Table 2, entries
10−14). Interestingly, the cross-coupling yield decreases with
increase of the alkyl moiety size of the primary alcohol solvent.
Various arylsiloxanes were also tested for the cross-coupling
with 4-methylbenzenediazonium tetrafluoroborate salt, and the
results are summarized in Table 3. Excellent yields were
Oxidative Addition. The active Pd(0) species from the
reduction of the divalent Pd(II) species by alcoholic solvent
have different configurations as shown in Scheme 2. Our
calculations indicate that the most stable Pd(0) species is 1a in
which the Pd(0) coordinates with an acetate anion and the
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a
Table 3. Cross-Coupling Reactions of Arenediazonium Tetrafluoroborate Salt with Various Organosilanes
a
Reaction conditions: organosilane (0.6 mmol), 4-methylbenzenediazonium tetrafluoroborate salt (0.5 mmol), Pd(OAc)2 (5 mol %), CH3OH (2
b
c
mL), 25 °C, 6 h. Isolated yields. The amount of dimethoxydiphenylsilane was 0.3 mmol.
NN double bond of the benzenediazonium cation. The
oxidative addition step is feasible since the activation energy is
only 10.7 kcal/mol for the oxidative addition from the 1c
configuration. The optimized structures of 1a, 1c, and the
oxidative addition transition state TS1-2 are shown in Figure 1.
The oxidative addition leads to the formation of the phenyl-
Pd(II) complex, which will release 20.5 kcal/mol. Similarly, the
oxidative addition may also lead to other benzenediazonium-
Pd(0) complexes (e.g., benzenediazonium-Pd(0) tetrafluor-
oborate) to form the corresponding phenyl-Pd(II) complexes.
Transmetalation. For the Hiyama reaction, the much
more reactive pentacoordinated arylsilicate anion can be in situ
formed from the tetracoordinated arylsilicate anion through the
nucleophilic attack of fluoride ion at the arylsiloxane.18 Thus,
we speculated that the BF4 anion may play a similar role to
form the pentacoordinated silicate to facilitate the cross-
coupling reaction. First, we tried to optimize the geometry of
the pentacoordinated silicate anion from the reaction of
phenyltrimethoxysilane and BF4 anion, but we failed to opti-
mize the geometric structures regardless of the initial distance
of the Si−F bond, suggesting that the pentacoordinated silicate
anion may not be stable for the reaction of BF4 anion with
phenyltrimethoxysilane. These results led us to search for other
possible mechanisms for the transmetalation between the
phenyl-Pd(II) complex and phenyltrimethoxysilane. The
possible transition states with their relative energies are
summarized in Scheme 3, and their optimized structures are
illustrated in Figure S1 of the Supporting Information.
not be the primary pathway due to the limited source of the
acetate anion only from the precatalyst Pd(OAc)2. The
calculations also indicate that the other favored route is the
attack of tetrafluoroborate anion on the Si atom from the back
side of phenyltrimethoxysilane. The transition state is shown in
TS2-3d with an activation energy of 17.4 kcal/mol (relative to
phenyl-Pd(II) tetrafluoroborate and phenyltrimethoxysilane).
The relatively low energy barrier could be attributed to the
stabilization by the coordination of Pd with one of the
methoxyl group of the phenyltrimethoxysilane.
Reductive Elimination. The resulting (phenyl)(phenyl)-
Pd(II) species undergoes reductive elimination to give the
cross-coupling product. The reductive elimination step is very
fast since the activation energy is less than 6 kcal/mol. The
optimized structures of relevant transition states are summar-
ized in Figure S2 of the Supporting Information.
Overall Mechanism. The calculated reactive intermediates
and free-energy contour diagram for the cross-coupling reaction
are summarized in Figure 2. The Pd(II) precatalyst is first
reduced into the active Pd(0) species which initiates the
catalytic cycle by reaction with arenediazonium salt to form the
aryl-Pd(II) intermediate and nitrogen gas. The resulting aryl-
Pd(II) intermediate will couple with phenyltrimethoxysilane to
afford the (aryl)(aryl)-Pd(II) species with the release of
SiR3OAc or FSiR3 and BF3. Reductive elimination of the biaryl
product will concomitantly regenerate the active Pd(0) species
to complete the catalytic cycle. Although there are two possible
pathways for the cross-coupling reaction, the reaction will
proceed via pathway 1 instead of pathway 2 provided that
acetate anion is present. Thus, we believe that the cross-
coupling reaction will predominantly proceed via pathway 1 in
the presence of acetate anion and the transmetalation step is
Our calculations clearly show that the most favored route is
the attack of the Si atom by one of the oxygen atoms of the
acetate anion, followed by the phenyl transfer from the Si to the
Pd via the six-membered transition state TS2-3b and the
related activation energy barrier is 21.4 kcal/mol. But this will
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a
Table 4. Cross-Coupling Reactions of Various Arenediazonium Tetrafluoroborate Salts with Dimethoxydiphenylsilane
a
Reaction conditions: diphenyldimethoxysilane (0.3 mmol), 4-methylbenzenediazonium tetrafluoroborate salt (0.5 mmol), Pd(OAc)2 (5 mol %),
b
solvent (2 mL), 25 °C, 6 h. Isolated yields.
the rate-limiting step regardless of the presence of the acetate
anion.
reaction has great prospects of applications in organic
syntheses. Theoretical analysis shows that both acetate and
tetrafluoroborate anions may be involved in the attack on the Si
atom for the rate-limiting transmetalation step of the catalytic
cycle.
CONCLUSIONS
■
In summary, we have demonstrated that the palladium-
catalyzed Hiyama cross-coupling reactions of arenediazonium
salts with organosilanes could afford the corresponding biaryls
in good yields under mild reaction conditions. The trans-
formation can tolerate either electron-donating or electron-
withdrawing functional groups. As part of our continuing
exploration for new chemistry of the arenediazonium salts, this
EXPERIMENTAL SECTION
■
General Remarks. All solvents are analytical grade and used
without further purification. 1H NMR spectra were recorded on a
400 MHz spectrometer using TMS as an internal standard. The
multiplicities are reported as follows: singlet (s), doublet (d), doublet
of doublets (dd), multiplet (m), and broad resonance (br). Mass
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spectra were obtained on an HRMS-EI instrument. Arenediazonium
salts were synthesized according to the literature procedures if they
were not commercially available.
Preparation of Arenediazonium Salts. To a 500 mL flask
containing 63 mL of HCl and 63 mL of water was added 0.25 mol of
aniline. Aniline hydrochloride crystals were formed at 0−5 °C, and
then 18 g of sodium nitrite in 40 mL water was added dropwise,
followed by addition of 40 g of sodium tetrafluoroborate in 80 mL of
water. The reaction mixture was allowed to stir for another 10 min at
temperature below 5 °C. The arenediazonium salt solids were filtered
out and then washed with 10 mL of 5% sodium tetrafluoroborate three
times, followed by 15 mL of methanol two times.
Scheme 1. General Catalytic Cycle of Hiyama Reaction
General Procedure. A solution of silyl ether (0.6 mmol) in
anhydrous methanol (2 mL) was slowly added to an oven-dried
Schlenk tube containing arenediazonium salts (0.5 mmol) and
Pd(OAc)2 (5 mol %). The resulting mixture was allowed to stir at
room temperature for 6 h, and the solid catalyst was then removed by
filtration. The reaction mixture was quenched with 10 mL of water and
then extracted three times with ethyl acetate (3 × 20 mL). The
combined organic layer was washed with water and saturated brine and
then dried over anhydrous Na2SO4. Solvent was removed under a
reduced pressure, and the cross-coupling products were purified by
silica gel chromatography with petroleum ether and ethyl acetate.
4-Methyl-1,1′-biphenyl (T3-1, CAS no. 644-08-6): 1H NMR (400
MHz, CDCl3, TMS) δ 7.55 (t, J = 6.8 Hz, 2 H), 7.38−7.48 (m, 4 H),
7.32 (t, J = 7.2 Hz, 1 H), 7.21 (d, J = 7.6 Hz, 2 H), 2.33 (s, 3 H);
HRMS (EI) calcd for C13H12 (M+) 168.0939, found 168.0936.
4,4′-Dimethyl-1,1′-biphenyl (T3-4, CAS no. 613-33-2): 1H NMR
(400 MHz, CDCl3, TMS) δ 7.47 (d, J = 8.0 Hz, 4 H), 7.45 (d, J =
7.6 Hz, 4 H), 2.37 (s, 6 H); HRMS (EI) calcd for C14H14 (M+)
182.1096, found 182.1099.
Scheme 2. Possible Structures for the Active Pd(0) Species
3-Fluoro-4′-methyl-1,1′-biphenyl (T3-5, CAS no. 72093-42-6): 1H
NMR (400 MHz, CDCl3, TMS) δ 7.44 (t, J = 8.0 Hz, 2 H), 7.28−7.35
(m, 2 H), 7.19−7.23 (m, 3 H), 7.02 (t, J = 8.0 Hz, 1 H), 2.35 (s, 3 H);
HRMS (EI) calcd for C13H11F (M+) 186.0841, found 186.0841.
4-Methyl-4′-(trifluoromethyl)-1,1′-biphenyl (T3-6, CAS no.
97067-18-0): 1H NMR (400 MHz, CDCl3, TMS) δ 7.65−7.72
(m, 4 H), 7.46 (d, J = 7.2 Hz, 2 H), 7.21 (d, J = 7.6 Hz, 2 H), 2.37 (s, 3
H); HRMS (EI) calcd for C14H11F3 (M+) 236.0813, found 236.0815.
2-(p-Tolyl)benzofuran (T3-7, CAS no. 25664-48-6): 1H NMR (400
MHz, CDCl3, TMS) δ 7.73 (d, J = 8.4 Hz, 2 H), 7.48−7.54 (m, 2 H),
7.17−7.26 (m, 4 H), 6.92 (s, 1 H), 2.36 (s, 3 H); HRMS (EI) calcd for
C15H12O (M+) 208.0888, found 208.0889.
3-Nitro-1,1′-biphenyl (T4-1, CAS no. 2113-58-8): 1H NMR (400
MHz, CDCl3, TMS) δ 8.45 (s, 1 H), 8.19 (d, J = 8.4 Hz, 1 H), 7.91
(t, J = 8.0 Hz, 1 H), 7.58−7.63 (m, 3 H), 7.50 (t, J = 7.2 Hz, 2 H), 7.43
(t, J = 7.6 Hz, 1 H); HRMS (EI) calcd for C12H9NO2 (M+) 199.0633,
found 199.0631.
Figure 1. Optimized structures for the Pd(0) complexes 1a and 1c and the oxidative addition transition state TS1-2.
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a
Scheme 3. Possible Transition States for Transmetalation and Their Energies Relative to Phenyl-Pd(II) acetate and Phenyltrimethoxysilane
a
The values in parentheses are relative to phenyl-Pd(II) tetrafluoroborate and phenyltrimethoxysilane.
Figure 2. Calculated free energy contour diagram for the Pd-catalyzed cross-coupling reaction of phenyldiazonium tetrafluoroborate salt with
phenyltrimethoxysilane. Energies are in kcal/mol. The values in parentheses are relative to phenyldiazonium-Pd tetrafluoroborate 1a.
4-Nitro-1,1′-biphenyl (T4-2, CAS no. 92-93-3): 1H NMR (400
MHz, CDCl3, TMS) δ 8.28 (d, J = 8.4 Hz, 2 H), 7.72 (d, J = 9.2 Hz,
2 H), 7.62 (d, J = 6.8 Hz, 2 H), 7.42−7.51 (m, 3 H); HRMS (EI) calcd
for C12H9NO2 (M+) 199.0633, found 199.0634.
4-Chloro-1,1′-biphenyl (T4-3, CAS no. 644-08-6): 1H NMR (400
MHz, CDCl3, TMS) δ 7.56 (t, J = 6.8 Hz, 2 H), 7.40−7.48 (m, 4 H),
7.32 (t, J = 7.2 Hz, 1 H), 7.22 (d, J = 7.6 Hz, 2 H); HRMS (EI) calcd
for C12H9Cl (M+) 188.0393, found 188.0396.
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4-Bromo-1,1′-biphenyl (T4-4, CAS no. 92-66-0): 1H NMR (400
MHz, CDCl3, TMS) δ 7.58 (d, J = 7.2 Hz, 1 H), 7.51−7.54 (m, 3 H),
7.39−7.43 (m, 3 H), 7.30−7.37 (m, 2 H); HRMS (EI) Calcd for
C12H9Br (M+) 231.9888, Found 231.9887.
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(400 MHz, CDCl3, TMS) δ 7.54 (d, J = 8.4 Hz, 4 H), 7.41 (t, J =
7.6 Hz, 2 H), 7.30 (t, J = 7.2 Hz, 1 H), 6.98 (d, J = 8.4 Hz, 2 H), 3.85
(s, 3 H); HRMS (EI) calcd for C13H12O (M+) 184.0888, found
184.0884.
2-Chloro-1,1′-biphenyl (T4-7, CAS no. 2051-60-7): 1H NMR (400
MHz, CDCl3, TMS) δ 7.59 (d, J = 8.4 Hz, 2 H), 7.40−7.49 (m, 4 H),
7.25−7.36 (m, 3 H); HRMS (EI) calcd for C12H9Cl (M+) 188.0393,
found 188.0391.
2,6-Dimethyl-1,1′-biphenyl (T4-8, CAS no. 3976-34-9): 1H NMR
(400 MHz, CDCl3, TMS) δ 7.60 (d, J = 7.2 Hz, 3 H), 7.44 (t, J = 7.6
Hz, 3 H), 7.34 (t, J = 7.2 Hz, 1 H), 6.92 (t, J = 7.2 Hz, 1 H), 2.29 (s, 6
H); HRMS (EI) Calcd for C14H14 (M+) 182.1096, Found 182.1097.
3,5-Dimethyl-1,1′-biphenyl (T4-9, CAS no. 17057-88-4): 1H NMR
(400 MHz, CDCl3, TMS) δ 7.56−7.60 (m, 3 H), 7.39−7.45 (m, 3 H),
7.34 (t, J = 7.2 Hz, 1 H), 7.20 (t, J = 8.0 Hz, 1 H), 2.38 (s, 3 H), 2.29
(s, 3 H); HRMS (EI) calcd for C14H14 (M+) 182.1096, found
182.1098.
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1-Phenylnaphthalene (T4-10, CAS no. 605-02-7): 1H NMR (400
MHz, CDCl3, TMS) δ 7.90 (t, J = 8.0 Hz, 1 H), 7.59 (d, J = 8.4 Hz,
2 H), 7.48−7.53 (m, 3 H), 7.41−7.47 (m, 5 H), 7.33 (t, J = 7.2 Hz,
1 H); HRMS (EI) calcd for C16H12 (M+) 204.0939, found 204.0937.
COMPUTATIONAL METHODS
■
All calculations were carried out with the Gaussian 09 programs19 in
the Supercomputing Center of the University of Science and
Technology of China. The geometrical optimizations in methanol
were performed using Becke’s three-parameter exchange functional
and the nonlocal correlation functional of Lee, Yang, and Parr
(B3LYP)20 with the 6-31G(d) basis set for all atoms except Pd, which
was described by the LANL2DZ basis set, in collaboration with the
polarized continuum model (PCM)21 with Bondi radii. The optimized
structures of the reactants, intermediates, and products were
confirmed to be real minima on the potential energy surface by the
frequency calculations. Transition states were identified as having one
imaginary frequency in the Hessian matrix. Single-point energy
calculations were performed on the stationary points by using the
M06 method with a larger basis set, i.e., LANL2DZ with an added f-
polarization shell for Pd and 6-311++G(2df,2p) for the other
elements, in collaboration with the same solvation model as
optimization. All solution-phase free energies reported in the paper
correspond to the reference state of 1 mol/L, 298.15 K.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H NMR spectra for the cross-coupling products, optimized
structures of the transitional states, and computational details
including energy properties and Cartesian coordinates of
reactants, intermediates, and their transition states. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: qichenze@usx.edu.cn.
ACKNOWLEDGMENTS
■
We acknowledge financial support from the Natural Science
Foundation (Project Nos. Y4080448 and Y4080450) of
Zhejiang Province, China.
9267
dx.doi.org/10.1021/jo201437j|J. Org. Chem. 2011, 76, 9261−9268

The Journal of Organic Chemistry
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