Efficient cross-coupling of aryl/alkenyl triflates with acyclic secondary alkylboronic acids

Article abstract of DOI:10.1039/c7ob02531a

Aryl-secondary alkyl cross-coupling with aryl sulfonate esters as coupling partners remains a significant challenge. Efficient cross-coupling between aryl/alkenyl triflates and acyclic secondary alkylboronic acids is realized for the first time to provide a series of sterically congested acyclic secondary alkyl arenes/olefins in good to excellent yields. The employment of sterically bulky P,PO ligand L1/L2 is crucial for the high yields and selectivities. The method has enabled a concise and 4-step synthesis of a key intermediate of male contraceptive agent and PAF antagonist gossypol.

Full text of DOI:10.1039/c7ob02531a

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Efficient Cross-Coupling of Aryl/Alkenyl Triflates with Acyclic
Secondary Alkylboronic Acids†
Tengda Si,a Bowen Li,b Wenrui Xiong,b Bin Xu‡a and Wenjun Tang‡b
Received 00th January 20xx,
Accepted 00th January 20xx
Aryl-secondary alkyl cross-coupling with aryl sulfonate esters as coupling partners remains a significant challenge. Efficient
cross-coupling between aryl/alkenyl triflates and acyclic secondary alkylboronic acids is realized for the first time to
provide a series of sterically congested acyclic secondary alkyl arenes/olefins in good to excellent yields. The employment
of sterically bulky P,P=O ligand L1/L2 is crucial for the high yields and selectivities. The method has enabled a concise and
DOI: 10.1039/x0xx00000x
www.rsc.org/
4-step synthesis of
a
key intermediate of male contraceptive agent and PAF antagonist gossypol.
with very low yields (4% and 12%) are reported on such
couplings (Scheme 1a and 1b).7 The challenges mainly reside
Introduction
Sterically congested secondary alkyl/isopropyl arenes exist in
numerous biologically important natural products or drugs
(Figure 1).1 Their preparation often requires a multiꢀstep
sequence i.e. an initial formation of an acyl arene by Friedelꢀ
Crafts acylation or nucleophilic substitution with a metal
reagent, followed by methylation with a lithium/Grignard
reagent, and finally hydrogenolysis to remove a benzylic
hydroxyl group. Alternatively, the sterically hindered arylꢀ
secondary alkyl crossꢀcoupling in particular the Suzukiꢀ
Miyaura2,3 crossꢀcoupling has provided an attractive and
straightforward method. Nevertheless, there remain many
limitations in the substrate scope of arylꢀsecondary alkyl crossꢀ
coupling.4 Besides the critical chemoꢀselectivity issue
(inhibition of isomerization and reduction sideꢀproducts), the
current substrate scope is mostly limited to aryl halides.
Because of the ready availability and abundance of phenol and
ketone derivatives, it is of significant importance to develop
efficient crossꢀcouplings between aryl/alkenyl triflates and
acyclic secondary alkylboronic acids. Herein we report our
OH
OH
OH
H
HO
CHO
H
O
H
HO
OH
OH
CHO
Abietic acid
Totaradiol
O
O
H
H
OH
OH
OH
OH
HO
OH
H
OH
(+)-Anhydroryanodol
O
(-)-Cyanthiwigin F
Gossypol
Figure 1. Biologically interesting natural products with isopropyl aryl
moieties
.
progress in crossꢀcoupling between aryl/alkenyl triflates and in two folds: (a) The arylꢀsecondary alkyl SuzukiꢀMiyaura
acyclic secondary alkylboronic acids to provide a series of crossꢀcouplings often complicate with reduction and
sterically congested acyclic secondary alkyl arenes in good to isomerization sideꢀreactions due to the presence of βꢀhydrogen
excellent yields.
in the alkyl group;4a(b) The aryl/alkenyl triflates tend to be
hydrolyzed during the reaction. Our research group aimed to
address these issues by designing and developing effective
phosphorus ligands. By employing a sterically bulky P,P=O
ligand L1 or L2, we developed an efficient crossꢀcoupling
between sterically hindered aryl halides and acyclic secondary
alkylboronic acids in high yields and excellent chemoꢀ
Despite the numerous applications of aryl sulfonate esters in
arylꢀaryl5 and arylꢀprimary alkyl6 crossꢀcoupling, few successes
have been achieved in arylꢀsecondary alkyl crossꢀcoupling with
aryl sulfonate esters as starting materials. Only a few examples
selectivity.8 The role of P=O moiety in ligand L1
/L2 was to
provide a hemilabile coordination to the palladium so that the
isomerization and reduction sideꢀproducts could be effectively
inhibited. The success in our previous study with L1/L2 as the
ligand prompted us to investigate the challenging crossꢀ
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aThe reactions were performed under nitrogen in toluene (2 mL) at
coupling between aryl/alkenyl triflates and secondary alkyl
boronic acids. Herein we detailed our results.
o
110 C for 12 h in the presence of 1 mol % [ Pd(cinnamyl)Cl]2 and 4
mol % L1 with 1 (0.25 mmol), 2 (0.5 mmol), and K3PO4•H2O (0.75
mmol). bConversions were analyzed by reversed phase HPLC on a C-
18 column. cIsolated yields. diPr/nPr ratios were determined by 1H
NMR spectroscopy.
by employing various commercially available phosphorus
ligands (Table 1). The reactions were performed under nitrogen
o
in toluene at 110 C for 12 h at 2 mol % palladium loading. As
shown in Table 1, various phosphorus ligands provided
dramatically different results. Not surprisingly, the desired
coupling product
AntPhos10 as the ligand (entry 1ꢀ2). Besides the isomerization
and the reduction sideꢀproducts and , severe formation of the
hydrolysis product was also observed. Excitingly, ligand L1
provided the desired coupling product in 83% yield (entry 3),
3
was isolated in <5% yield with BIꢀDIME9 or
4
5
6
3
once again demonstrating the special property of the P,P=O
ligand in promoting the arylꢀalkyl crossꢀcoupling. A related
Scheme 1. Cross-coupling of aryl sulfonate ester with secondary alkyl
boron reagents.
ligand L2
,
however, provided an inferior yield and
series of
regioselectivity (entry 4). For comparison,
a
phosphorus ligands which were often applied in arylꢀaryl
SuzukiꢀMiyaura coupling were employed for study (entries 5ꢀ
13). Under similar conditions, none of these ligands provided
Results and discussion
the desired product
power of L1 for the success of this reaction. While some
ligands such as DPPF, SPhos11, XPhos12, PCy313, and PPh3
provided low yields of the isomerization sideꢀproduct
6, 9ꢀ10, 12ꢀ13), the rest only led to the formation of
3, further indicating the uniqueness and
We studied the SuzukiꢀMiyaura coupling between 2ꢀ
methylnaphthalenꢀ1ꢀyl triflate (1a) and isopropylboronic acid
(2)
4
(entries
and
5
6.
The employment of aryl triflate 1a was crucial for the reactivity,
while a low yield or no formation of product was observed with
tosylate 1b and mesylate 1c (entries 14ꢀ15).
Table 1. Cross-coupling between aryl triflate 1 and isopropylboronic
acid 2
We then examined the substrate scope of the arylꢀsecondary
alkyl crossꢀcoupling. As can be seen in Table 2, a series of
monoꢀ or diꢀorthoꢀsubstituted aryl triflates were successfully
coupled with isopropylboronic acid or secꢀbutylboronic acid
with the PdꢀL1/L2 catalyst to form the corresponding coupling
products in good yields (45ꢀ92%) and excellent iPr/nPr ratios.
Moderate to high yields (50ꢀ92%) were achieved for a range of
monoꢀorthoꢀsubstituted isopropyl arenes (3c-3l). A variety of
orthoꢀsubstituents such as methyl, ethyl, isopropyl, methoxy,
trifluoromethyl, and formyl groups were compatible. Functional
groups such as cyano, Boc, and indole moieties were well
tolerated. A series of diꢀorthoꢀsubstituted acyclic secondary
alkyl arenes with various substituents and functionalities were
also formed successfully in high yields and excellent iPr/nPr
Conv.
(%)b
Entrya
L
Yield (%)
R’
3c
<1
2
83
69
0
4c
28
35
6
23
0
3:4d
1:28
1:17
14:1
3:1
5b
11
9
0
0
6c
58
50
5
6
75
selectivities (3a, 3m-3q). Importantly, product 3p was isolated
1
2
3
4
5
BI-DIME
AntPhos
L1
L2
BINAP
Tf
Tf
Tf
Tf
Tf
100
100
100
100
100
in 85% yield at a gram scale, demonstrating the practicality of
the coupling. For 2ꢀmethoxyꢀ1ꢀnaphthyl triflate (3q), ligand L1
formed a low iPr/nPr ratio (1.5:1) most likely due to the
coordinative ability of the orthoꢀmethoxy group. Fortunately,
ligand L2 containing the dimethylamino moiety in its structure
provided a good iPr/nPr selectivity (12:1), which was consistent
with our previous report6 on crossꢀcoupling of aryl halides. Secꢀ
Butylboronic acids were also employed successfully to form the
corresponding secondary alkyl arenes in high yields and
excellent selectivities (3r-3t). However, no desired coupling
product was formed in the cases of a substrate containing an
25
--
--
--
--
--
--
--
--
--
--
--
6
7
8
DPPF
DPPP
DPPB
Tf
Tf
Tf
100
88
0
0
0
13
0
19
0
68
80
93
100
0
5
9
SPhos
XPhos
XantPhos
PCy3
PPh3
L1
Tf
Tf
Tf
Tf
Tf
100
95
86
100
100
10
0
0
0
0
0
5
0
1
3
0
14
4
0
12
11
0
25
51
1
87
80
12
57
44
4
10
11
12
13
14
15
Ts
Ms
L1
20
0
0
18
2 | J. Name., 2012, 00, 1-3
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ciPr/nPr or secBu/nBu (3r-3t) ratios were determined by HPLC on a
orthoꢀnitro (3v) or ꢀtertꢀbutyl group (3w), or both an ortho
methyl and an orthoꢀcyano substituents (3x).
ꢀ
C18 reverse-phase column or by 1H NMR spectroscopy. d2 mol %
[Pd(cinnamyl)Cl]2 and
[Pd(cinnamyl)Cl]2 and 8 mol % L1. gGram scale.
8 mol % % %
L2. e4 mol L2. f2 mol
Table 3. Sterically hindered alkenyl-alkyl cross-couplingsa,b,c
Table 2. Cross-coupling between aryl triflates and secondary alkyl
boronic acids: substrate scopea,b,c
aUnless otherwise specified, the reactions were performed under
nitrogen in toluene (2 mL) at 110 oC for 12 h in the presence of 1 mol %
[Pd(cinnamyl)Cl]2 and
4 mol % L1 with triflate (0.25 mmol),
isopropylboronic acid (0.5 mmol), and K3PO4•H2O (0.75 mmol).
bIsolated yields. ciPr/nPr ratios were determined by HPLC on a C18
reverse-phase column or by 1H NMR spectroscopy. d2 mol %
[Pd(cinnamyl)Cl]2 and 8 mol % L1.
Because of the ready accessibility of alkenyl triflates from
corresponding ketones, the crossꢀcoupling between alkenyl
triflates and isopropylboronic acids can provide an important
method for the synthesis of sterically hindered triꢀ or tetraꢀ
substituted olefins, which are otherwise tedious to prepare.4 As
shown in Table 3, a series of alkenyl triflates were coupled
smoothly with isopropylboronic acid to give the corresponding
alkenes in moderate to good yields. Cyclic olefinic triflates with
5, 6, and 7ꢀmembered rings were all applicable to form the
corresponding coupling products in high yields and excellent
selectivities (4a-4c). Substrates bearing oxygenꢀ or nitrogenꢀ
containing heterocycles were well tolerable
tetrasubstituted olefin was also formed successfully in 97%
yield with a high Pr/ Pr ratio (4f).
(4d-4e). A
i
n
The crossꢀcoupling method enabled a concise and 4ꢀstep
synthesis of compound 11, the key intermediate of male
contraceptive agent and PAF antagonist gossypol (Scheme 2).14
Thus, DielsꢀAlder reaction between diene
7
and
dimethoxyquinone provided benzoquinone in 82% yield.
8
9
Reduction of 9 under action of BF3.Et2O and Et3SiH followed
by triflate formation provided 10 in 60% overall yield through 2
steps. Crossꢀcoupling of 10 with isopropylboronic acid with Pdꢀ
L2 as the catalyst provided the key gossypol intermediate 11 in
62% yield with the iPr/nPr ratio of 5.5 /1, which constituted the
shortest sequence to date to prepare gossypol intermediate 11
.
aUnless otherwise specified, the reactions were performed under
nitrogen in toluene (2 mL) at 110 oC for 12 h in the presence of 1 mol %
[Pd(cinnamyl)Cl]2 and 4 mol % L1 with triflate (0.25 mmol), boronic
acid (0.5 mmol), and K3PO4•H2O (0.75 mmol). bIsolated yields.
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7890A/5975C Series GC/MSD mass spectrometer. HPLC yield
were determined on Agilent 1200 Infinity Series.
General procedure for the synthesis of compounds 3a–
u (Table 2) and 4a-f (Table 3)
To a mixture of aryl/alkenyl triflates (0.25 mmol), alkylboronic
acid (0.5 mmol), potassium phosphate tribasic monohydrate
(0.75 mmol), [Pd(cinnamyl)Cl]2 (0.0013 mmol, 2.0 mol % Pd),
phosphorus ligand (L1 or L2, 4.0 mol %, Pd :
L = 1 : 2) was
charged dry toluene (2 mL). The mixture was pumped and
refilled with nitrogen for three times. The resulting mixture was
Scheme 2. Synthesis of gossypol intermediate 11 through aryl alkyl
cross-coupling strategy. a) AcOH, DCM, rt, 82%; b) i) BF3.Et2O,
Et3SiH; ii) Tf2O, Et3N, DCM; 60% (2 steps); c) iPrB(OH)2,
[Pd(cinnamyl)Cl]2 (1 mol %), L2 (4 mol %), toluene, 62%, (iPr:nPr =
5.5 :1).
stirred at 110
℃ under nitrogen for 12 h, and then cooled to
room temperature, partitioned with water (2 mL) and
dichloromethane (3 mL). The organic layer was separated,
dried over sodium sulfate, concentrated, and purified by silica
gel column chromatography (hexanes/EtOAc as eluent) to
provide the coupling product. The
iPr/nPr ratios were
determined by HPLC on a C18 reversed phase HPLC column
or by 1H NMR.
Conclusions
Characterization data for the products 3a–u , 4a–f and 11
In summary, we demonstrated for the first time the crossꢀ
coupling between various sterically hindered aryl/alkenyl
triflates and acyclic secondary boronic acids to form a series of
sterically congested acyclic secondary alkyl arenes and olefins
in moderate to good yields and excellent chemoselectivities.
1-Isopropyl-2-methylnaphthalene(3a)
：
1H NMR (500 MHz,
CDCl3) δ 8.30 (d, J = 8.1 HZ, 1H), 7.83 (d, J = 8.0 HZ, 1H), 7.63 (d,
J = 8.3 HZ, 1H), 7.40~7.49 (dt, J = 29.3, 7.2 HZ, 2H), 7.30 (d, J =
8.4 HZ, 1H), 3.90 (s, 1H), 2.58 (s, 3H), 1.60 (d, J = 7.0 Hz, 12H);
13C NMR (125 MHz, CDCl3) δ 140.9, 133.0, 132.5, 131.85, 129.5,
125.6, 124.2, 29.4, 21.8(d, J = 20.3 Hz); EIꢀMS: m/z 184.0 [M]+;
HRMS (EI) m/z calcd for C14H16 (M): 184.1252, found: 184.1246.
Ligands L1/L2 played a crucial role in enabling the high yields
and selectivities of this aryl/alkenylꢀsecondary alkyl Suzukiꢀ
Miyaura crossꢀcoupling. This method enabled a concise and 4ꢀ
step synthesis of gossypol intermediate 11. Because of the
ready accessibility of aryl/alkenyl triflates from corresponding
4-Isopropylbenzaldehyde(3b)
：
1H NMR (500 MHz, CDCl3) δ
9.97 (s, 1H), 7.81 (d, J =8.0 Hz, 2H), 7.39 (d, J =8.1 Hz, 2H), 2.99
(septet, J = 6.9 HZ,1H), 1.29 (d, J = 6.9 Hz, 6H); 13C NMR (125
phenol/ketone precursors, this method provides expedite access MHz, CDCl3) δ 192.0, 156.2, 134.5, 130.0, 127.1, 34.5, 23.6; EIꢀ
MS: m/z 148.0 [M]+; HRMS (EI) m/z calcd for C10H12O (M):
148.0837, found: 148.0838.
to sterically hindered secondary alkyl arene and olefin moieties,
which should be highly valuable for the synthesis of natural
products and drugs.
1,2-Diisopropylbenzene(3c) ： 1H NMR (500 MHz, CDCl3)
δ7.26~7.29 (m, 2H), 7.18~7.21 (m, 2H), 3.31 (septet, J = 6.8
HZ,2H), 1.26 (d, J = 6.9 Hz, 12H); 13C NMR (125 MHz, CDCl3) δ
145.5, 125.8, 125.0, 28.1, 24.1; EIꢀMS: m/z 162.0 [M]+; HRMS (EI)
m/z calcd forC12H18 (M): 162.1409, found: 162.1415.
Experimental section
General
4-Isopropyl-3-(trifluoromethyl)benzonitrile (3d)： 1H NMR (500
MHz, CDCl3) δ 7.89 (t, J = 0.7 HZ,1H), 7.79 (dd, J = 8.2, 1.4 Hz,
1H), 7.61 (d, J = 8.2 Hz, 1H), 3.40 (septet, J = 6.6 HZ,1H), 1.28 (d, J
= 6.8 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 153.9, 135.4, 129.7
(q, J = 6.1 Hz), 128.7, 122.4, 117.9, 110.3, 29.9, 24.0 ; 19F NMR
(376 MHz, CDCl3) δ ꢀ59.9; EIꢀMS: m/z 213.1 [M]+; HRMS (EI) m/z
calcd for C11H10F3N (M): 213.0765, found: 213.0773.
All reactions were carried out under nitrogen atmosphere unless
otherwise specified. Unless otherwise noted, commercialized
reagents were used without further purifications. Toluene was
purchased from SigmaꢀAldrich Chemical Co. All other solvents
were purified and dried according to standard methods prior to
use. 1H NMR, 19F NMR and 13C NMR data were recorded on a
BrukerꢀUltrashield PLUS400 NMR or a 500 MHz Agilent
spectrometer with CDCl3 as the solvent. 1H chemical shifts
were referenced to CDCl3 at 7.26 ppm. 13C chemical shifts were
referenced to CDCl3 at 77.14 ppm and obtained with 1H
decoupling. 31P chemical shifts were referenced to 85% H3PO4
3-Isopropyl-4-methoxybenzaldehyde(3e)
：
1H NMR (500 MHz,
CDCl3) δ 9.87 (s, 1H), 7.76 (d, J = 2HZ, 1H), 7.69~7.71 (m, 1H),
6.94 (d, J = 8.4 HZ, 1H ), 3.91 (s, 1H), 3.32 (septet, J = 6.8 HZ, 1H),
1.23 (d, J = 6.9 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 191.3,
162.0, 137.9, 130.5, 129.7, 127.1, 110.0, 55.6, 26.7, 22.4; EIꢀMS:
m/z 178.0 [M]+; HRMS (EI) m/z calcd for C11H14O2 (M): 178.0994,
found: 178.1000.
1
in D2O at 0.0 ppm as external standard and obtained with H
decoupling. Multiplicities are abbreviated as follows: singlet (s),
doublet (d), triplet (t), quartet (q), doubletꢀdoublet (dd), triplet ꢀ
doublet (td), quintet (quint), sextet (sextet), septet (septet),
multiplet (m), and broad (br). MS was measured on Agilent
1-Isopropylbenzene(3f)：1H NMR (500 MHz, CDCl3) δ 8.23 (d,
1H), 7.93~7.96 (m, 1H), 7.79 (d, 1H), 7.50~7.62 (m, 4H), 3.85
(septet, J = 6.8 HZ, 1H), 1.50 (d, J = 6.9 Hz, 12H); 13C NMR (125
MHz, CDCl3) δ 144.59, 133.90, 131.35, 128.89, 127.85, 126.26,
125.78, 125.63, 125.61, 125.19, 123.27, 121.66, 28.50, 23.53 ; EIꢀ
4 | J. Name., 2012, 00, 1-3
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MS: m/z 170.0 [M]+; HRMS (EI) m/z calcd for C13H14 (M): Isopropyl-2-methoxynaphthalene(3q)
ARTICLE
：
1H NMR (500 MHz,
170.1096, found: 170.1100.
CDCl3) δ 8.21 (d, J = 8.7 HZ, 1H), 7.83 (d, J = 8.2 HZ, 1H), 7.75 (d,
J = 9.0 HZ, 1H), 7.50 (t, J = 8.0 HZ, 1H), 7.37 (t, J = 7.8 HZ, 1H),
7.31 (d, J = 9.0 HZ, 1H), 4.01 (s, 1H), 3.98 (s, 3H), 1.54 (d, J = 7.2
Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 132.6, 129.7, 129.3, 128.8,
127.7, 125.9, 123.4, 123.1, 114.8, 56.6, 26.6, 21.3; EIꢀMS: m/z 200.1
[M]+; HRMS (EI) m/z calcd for C14H16O (M): 200.1201, found:
200.1197.
Tert-butyl 4-isopropyl-1H-indole-1-carboxylate (3g)：1H NMR
(500 MHz, CDCl3) δ 8.04 (d, J = 7.9 HZ, 1H), 7.63 (d, J = 3.6 HZ,
1H), 7.31 (t, J = 7.9 HZ, 1H), 7.14 (d, J = 7.5HZ, 1H), 6.70 (d, J =
3.7HZ, 1H), 3.35 (septet, J = 6.9 HZ, 1H), 1.70 (d, J = 3.8HZ, 9H),
1.38 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 149.8,
141.2, 128.9, 125.2, 124.4, 118.5, 115.1, 112.8, 105.5, 83.4, 30.9,
28.2, 23.2; EIꢀMS: m/z 259.0 [M]+; HRMS (EI) m/z calcd for (S)-1-(sec-butyl)naphthalene(3r)：1H NMR (500 MHz, CDCl3)
C16H21NO2 (M): 259.1572, found: 259.1569.
δ8.13 (d, J = 8.9 HZ, 1H), 8.13 (dd, J = 7.9, 0.7 HZ, 1H), 7.70 (d, J =
8.1 HZ, 1H), 7.43~7.53 (m, 3H), 7.37~7.40 (m, 1H), 3.52 (sextet, J =
7.0 HZ,1H), 1.82~1.90 (m, 1H), 1.67~1.77 (m, 1H), 1.38 (d, J = 6.9
Hz, 3H), 0.93 (t, J = 7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ
143.7, 133.9, 131.8, 128.9, 126.1, 125. 6,125.5, 125.2, 123.2, 122.4,
35.3, 30.6, 21.2, 12.3; EIꢀMS: m/z 184.0 [M]+; HRMS (EI) m/z calcd
for C14H16 (M): 184.1252, found: 184.1251.
1-Isopropyl-2-methoxy-4-methylbenzene(3h)
：
1H NMR (500
MHz, CDCl3) δ 7.11 (d, J = 7.7 Hz, 1H), 6.76 (d, J = 7.8 Hz, 1H),
6.68 (s, 1H), 3.82 (s, 3H), 3.29 (septet, J = 6.9 HZ, 1H), 2.34 (s, 3H),
1.21 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 156.6,
136.3, 134.0, 125.8, 121.0, 111.4, 55.3, 26.4, 22.8, 21.4; EIꢀMS: m/z
164.1 [M]+; HRMS (EI) m/z calcd for C11H16O (M): 164.1201,
found: 164.1208.
(S)-4-(sec-butyl)-3-methoxybenzonitrile(3s)
：
1H NMR (500 MHz,
CDCl3) δ 7.22 (s, 2H), 7.05 (s, 1H), 3.84 (s, 3H), 3.13 (sextet, J =
7.1 HZ, 1H), 1.52~1.64 (m, 2H), 1.17 (d, J = 7.0 HZ, 3H), 0.82 (t, J =
7.4 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 157.2, 142.2, 127.6,
124.9, 119.4, 113.3, 110.0, 55.7, 33.8, 29.5, 20.1, 12.1; EIꢀMS: m/z
189.0 [M]+; HRMS (EI) m/z calcd for C12H15NO (M): 189.1154,
found: 189.1158.
4-Isopropyl-3-methoxybenzonitrile(3i)
：
1H NMR (500 MHz,
CDCl3) δ 7.29~7.35 (m, 2H), 7.12 (d, J =1.3Hz, 1H), 3.92 (s, 1H),
3.41 (septet, J = 6.9 HZ,1H), 2.27 (d, J = 7.0 Hz, 6H); 13C NMR
(125 MHz, CDCl3) δ 156.8, 143.1, 126.8, 124.9, 119.2, 113.0,
110.0, 55.6, 27.0, 22.2; EIꢀMS: m/z 175.0 [M]+; HRMS (EI) m/z
calcd for C11H13NO (M): 175.0997, found: 175.0994.
(S)-4-(sec-butyl)-3,5-dimethylbenzaldehyde(3t)
：
1H NMR (500
4-Isopropyl-3-methoxybenzaldehyde(3j)
：
1H NMR (500 MHz,
MHz, CDCl3) δ 9.88~9.95 (d, 1H), 7.48 (d, J = 7.5 Hz, 2H), 3.22
(sextet, J = 7.4 HZ,1H), 2.45 (s, 6H), 1.40 (dd, J = 7.3, 0.4 Hz, 6H);
13C NMR (125 MHz, CDCl3) δ 192.4, 150.8, 137.4, 133.8, 129.4,
37.4, 27.8, 21.7, 18.3, 13.0; EIꢀMS: m/z 190.0 [M]+; HRMS (EI) m/z
calcd for C13H18O (M): 190.1358, found: 190.1361.
CDCl3) δ 9.93 (s, 1H), 7.35~7.42(m, 3H), 3.90 (s, 3H), 3.38 (septet,
J = 6.9 HZ,1H), 1.23 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz,
CDCl3) δ 192.0, 157.3, 144.90, 135.4, 126.4, 124.7, 108.4, 55.5,
27.2, 22.3; EIꢀMS: m/z 178.0 [M]+; HRMS (EI) m/z calcd for
C11H14O2 (M): 178.0994, found: 178.0993.
2-methoxy-4-methyl-1-phenethylbenzene (3u) ：1H NMR (500
MHz, CDCl3) δ 7.32~7.36 (m, 2H), 7.22~7.29 (m, 3H), 7.05 (d, J =
7.3 Hz, 1H), 6.76 (d, J = 7.5 Hz, 2H), 3.87 (s, 3H), 2.90~2.98 (m,
4H), 2.40 (s, 3H); 13C NMR (125 MHz, CDCl3) δ157.5, 142.7,
137.1, 129.7, 128.6, 128.3, 127.3, 125.8, 121.0, 111.4, 55.3, 36.5,
32.3, 21.6; EIꢀMS: m/z 226.0 [M]+; HRMS (EI) m/z calcd for
C16H18O (M): 226.1358, found: 226.1355.
2-Isopropyl-5-methoxybenzaldehyde(3k)
：
1H NMR (500 MHz,
CDCl3) δ 9.88 (s, 1H), 7.76 (d, J = 2.1 Hz, 1H), 7.70 (d, J = 8.4, 2.1
Hz, 1H), 6.95 (d, J = 8.4 Hz , 1H), 3.92 (s, 3H), 3.33 (septet, J = 7.0
HZ,1H), 1.23 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ
191.4, 162.1, 138.1, 130.6, 129.8, 127.3, 110.2, 55.8, 26.8, 22.5; EIꢀ
MS: m/z EIꢀMS: m/z 178.0 [M]+; HRMS (EI) m/z calcd for
C11H14O2 (M): 178.0994, found: 178.0993.
2-Isopropyl-1H-indene(4a)： 1H NMR (500 MHz, CDCl3) δ 7.38
(d, J = 7.4 HZ, 1H), 7.28 (d, J = 6.7 HZ, 1H), 7.22 (t, J = 7.5 HZ,
1H), 7.10 (t, J = 7.4 HZ, 1H), 6.51 (s, 1H), 3.35 (s, 2H), 2.88 (septet,
J = 6.8 HZ, 1H), 1.23 (d, J = 6.9 Hz, 6H); 13C NMR (125 MHz,
CDCl3) δ 157.3, 145.7, 143.1, 126.4, 124.2, 123.7, 123.6, 120.1,
39.3, 30.2, 22.7; EIꢀMS: m/z 158.0 [M]+; HRMS (EI) m/z calcd for
C12H14 (M): 158.1096, found: 158.1102.
4-Isopropyl-3-methylbenzaldehyde(3l)
：
1H NMR (500 MHz,
CDCl3) δ 9.94 (s, 1H), 7.67~7.70(m, 1H), 7.65(s, 1H), 7.40 (d, J =
7.9 Hz, 1H), 3.20 (septet, J = 6.9 Hz, 1H), 2.41 (s, 3H), 1.25 (d, J =
6.9 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 192.2, 154.4, 136.0,
134.1, 131.4, 128.0, 125.4, 29.7, 22.9, 19.2; EIꢀMS: m/z 162.0 [M]+;
HRMS (EI) m/z calcd for C11H14O (M): 162.1045, found: 162.1046.
2-Isopropyl-1,3-dimethylbenzene(3m) ： 1H NMR (500 MHz,
CDCl3) δ 6.90 (s, 2H), 3.50(septet, J = 7.3 HZ,1H), 2.45 (s, 6H),
2.33 (s, 3H), 1.42 (d, J = 7.3 Hz, 6H); 13C NMR (125 MHz, CDCl3)
δ 144.1, 136.0, 128.0, 125.4, 29.5, 21.5, 20.8 ; EIꢀMS: m/z 148.0
[M]+; HRMS (EI) m/z calcd for C11H16 (M): 148.1252, found:
148.1250.
4-Isopropyl-1,2-dihydronaphthalene(4b)： 1H NMR (500 MHz,
CDCl3) δ 7.33 (d, J = 7.8 HZ, 1H), 7.22 (td, J = 6.9, 2.2 HZ, 1H),
7.12~7.17 (m, 2H), 5.90 (td, J = 4.6 HZ, 1.0 1H), 2.91~3.00 (m, 1H),
2.72 (t, J = 7.8 HZ, 2H), 2.23~2.28 (m, 2H),1.18 (d, J = 6.8 HZ, 6H);
13C NMR (125 MHz, CDCl3) δ 142.6, 137.1, 135.0, 127.6, 126.2 (d,
J = 5.5 Hz), 122.4, 121.4, 28.6, 28.2, 23.0, 22.3; EIꢀMS: m/z 172.0
[M]+; HRMS (EI) m/z calcd for C13H16 (M): 172.1252, found:
172.1253.
2-Isopropyl-1,3,5-trimethylbenzene(3n)： 1H NMR (500 MHz,
CDCl3) δ 6.90 (s, 2H), 3.50(septet, J = 7.3 HZ, 1H), 2.45 (s, 6H),
2.33 (s, 3H), 1.42 (d, J = 7.3 Hz, 6H); 13C NMR (125 MHz, CDCl3)
δ 141.2, 136.0, 134.8, 130.1, 29.3, 21.5, 21.0, 20.7; EIꢀMS: m/z
162.0 [M]+; HRMS (EI) m/z calcd for C12H18 (M): 162.1409, found:
162.1411.
9-Isopropyl-6,7-dihydro-5H-benzo[7]annulene(4c) ： 1H NMR
(500 MHz, CDCl3) δ 7.23~7.17 (m, 2H), 7.14~7.20 (m, 2H), 5.88
(td, J = 7.3, 1.4 HZ, 1H), 2.80 (septet, J = 6.8 HZ, 1H), 2.51 (t, J =
7.1 HZ, 2H), 2.03 (m, 2H), 1.77 (q, J = 7.2 HZ, 2H), 1.07 (d, J = 6.8
HZ, 6H); 13C NMR (125 MHz, CDCl3) δ 147.9, 141.9, 141.4, 128.5,
126.4, 126.0, 125.9, 121.8, 34.6, 33.3, 32.1, 24.2, 22.3; EIꢀMS: m/z
186.1 [M]+; HRMS (EI) m/z calcd for C14H18 (M): 186.1409, found:
186.1408.
4-Isopropyl-3,5-dimethylbenzonitrile(3o)：1H NMR (500 MHz,
CDCl3) δ 7.24 (s, 2H), 3.45 (septet, J = 7.3 HZ,1H), 2.39 (s, 6H),
1.33 (d, J = 7.3 Hz, 6H); 13C NMR (125 MHz, CDCl3) δ 149.9,
137.3, 132.5, 119.2, 109.0, 29.8, 21.3, 20.3; EIꢀMS: m/z 173.0 [M]+;
HRMS (EI) m/z calcd for C12H15N (M): 173.1204, found: 173.1201.
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4-Isopropyl-2H-chromene(4d)：1H NMR (500 MHz, CDCl3) δ
7.24 (d, J = 7.7 HZ, 1H), 7.10~7.15 (m, 1H), 6.93 (t, J = 7.6 HZ,
1H), 6.85 (d, J = 8.1 HZ, 1H), 5.61 (t, J = 3.8 HZ, 1H), 4.74 (d, J =
3.8 HZ, 2H), 2.88 (septet, J = 6.4 HZ, 1H), 1.17 (d, J = 6.8 Hz, 6H);
13C NMR (125 MHz, CDCl3) δ 154.6, 140.4, 128.5, 123.5, 123.1,
121.1, 116.2, 114.9, 65.4, 27.6, 21.7; EIꢀMS: m/z 174.1 [M]+; HRMS
(EI) m/z calcd for C12H14O (M): 174.1056, found: 174.1051.
K. C. Nicolaou, P. G. Bulger and D. Sarlah, Angew. Chem., Int. Ed.
,
2005, 44, 4442. (j) F. Alonso, I. P. Beletskaya and M. Yus,
Tetrahedron, 2008, 64, 3047. (k) A. de Meijere, F. Diederich, Eds.
MetalꢀCatalyzed CrossꢀCoupling Reactions, Vol. 2, WileyꢀVCH,
Weinheim, 2004. (l) L. Ackermann, Ed. Modern Arylation Methods,
WileyꢀVCH, Weinheim, 2009. (m) C. C. C. J. Seechurn, M. O.
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2012, 23, 1132.
,
,
,
Tert-butyl 4-isopropyl-3,6-dihydropyridine-1(2H)-carboxylate
(4e)
：
1H NMR (500 MHz, CDCl3) δ 5.30 (d, J = 16.2 Hz, 1H), 3.84
(s, 2H), 3.46 (t, J = 5.5 Hz, 2H), 2.20 (septet, J = 7.1 HZ,1H), 2.04
(d, J = 5.7 Hz, 2H ), 1.46 (s, 9H ), 0.99 (d, J = 6.9 Hz, 6H ); 13C
NMR (125 MHz, CDCl3) δ 155.1, 142.5, 115.4, 79.4, 43.6, 40.0,
34.8, 28.6, 26.4, 21.1; EIꢀMS: m/z 225.0 [M]+; HRMS (EI) m/z calcd
for C13H23NO2 (M): 225.1025, found: 225.1023.
3
Recent papers on arylꢀaryl SuzukiꢀMiyaura couplings: (a) W. Shen,
Tetrahedron Lett., 1997, 38, 5575. (b) A. F. Littke and G. C. Fu,
Angew. Chem., Int. Ed., 1998, 37, 3387. (c) A. F. Littke, C. Dai and
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Ehrentraut and M. Beller, Angew. Chem., Int. Ed., 2000, 39, 4153. (e)
J. P. Stambuli, R. Kuwano and J. F. Hartwig, Angew. Chem., Int. Ed.
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2007, 13, 2701. (g) C. A. Fleckenstein and H. Plenio, J. Org. Chem.
,
,
,
4-Isopropyl-3-methyl-1,2-dihydronaphthalene(4f) ： 1H NMR
(500 MHz, CDCl3) δ 7.41 (d, J = 7.9 HZ, 1H), 7.19 (t, J = 7.3 HZ,
1H), 7.14 (d, J = 6.7 HZ, 1H), 7.09 (t, J = 7.3 HZ, 1H), 3.25 (septet, J
= 7.4 HZ, 1H), 2.66 (t, J = 7.6 HZ, 2H), 2.16 (d, J = 7.8 HZ, 2H),
1.98 (s, 3H), 1.35 (d, J = 7.4 Hz, 6H); 13C NMR (125 MHz, CDCl3)
δ 136.9, 136.4, 135.4, 133.1, 127.3, 125.8, 125.2, 123.7, 31.8, 29.2,
29.0, 21.5, 20.7; EIꢀMS: m/z 186.0 [M]+; HRMS (EI) m/z calcd for
C14H18 (M): 186.1456, found: 186.1361.
compound 11: 1H NMR (500 MHz, CDCl3) δ 7.47 (s, 2H), 6.61 (s,
1H), 3.98~3.97 (m, 4H), 3.88 (d, J = 2.7 Hz,3H), 2.49 (s, 3H), 1.50
(d, J = 6.0 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 154.9, 151.2,
135.0, 133.4, 128.9, 121.3, 115.7, 105.4, 100.1, 61.2, 55.6, 55.6,
28.1, 22.8, 22.3; EIꢀMS: m/z 274.4 [M]+; HRMS (EI) m/z calcd for
C17H22O3(M): 274.1569, found: 274.1570.
2008, 73, 3236. (h) C. M. So, C. P. Lau and F. Y. Kwong, Angew.
Chem., Int. Ed., 2008, 47, 8059. (i) C. M. So, W. K. Chow, P. Y.
Choy, C. P. Lau and F. Y. Kwong, Chem. Eur. J., 2010, 16, 7996. (j)
S. C. To and F. Y. Kwong, Chem. Commun., 2011, 47, 5079. (k) W.
Tang, N. D. Patel, G. Xu, X. Xu, J. Savoie, S. Ma, M.ꢀH. Hao, S.
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Hayashi, M. Konishi, Y. Kobori, M. Kumada, T. Higuchi and K.
Hirotsu, J. Am. Chem. Soc., 1984, 106, 158. (b) N. Miyaura, T.
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4
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
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4122. (j) A. Boudier and P. Knochel, Tetrahedron Lett., 1999, 40
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,
The work is supported by the Strategic Priority Research
Program of the Chinese Academy of Sciences XDB20000000,
CAS (QYZDYꢀSSWꢀSLH029), NSFCꢀ21432007, 21572246,
and K. C. Wong Education Foundation.
687. (k) T. Thaler, B. Haag, A. Gavryushin, K. Schober, E.
Hartmann, R. M. Gschwind, H. Zipse, P. Mayer and P. Knochel, Nat.
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