Palladium-catalyzed Mizoroki-Heck type reaction with aryl trialkoxysilanes using hydrazone ligands

Article abstract of DOI:10.1016/j.tet.2011.11.027

Palladium-catalyzed Mizoroki-Heck type reaction of olefines with aryl trialkoxysilanes gave the arylation products using a catalytic amount of hydrazone-Pd(OAc)₂ system with AgF at 60 °C in good yields.

Full text of DOI:10.1016/j.tet.2011.11.027

Tetrahedron 68 (2012) 429e432
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Palladium-catalyzed MizorokieHeck type reaction with aryl trialkoxysilanes using
hydrazone ligands
*
Takashi Mino , Masanori Shibuya, Saori Suzuki, Kiminori Hirai, Masami Sakamoto, Tsutomu Fujita
Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Palladium-catalyzed MizorokieHeck type reaction of olefines with aryl trialkoxysilanes gave the ar-
Received 30 September 2011
Received in revised form 7 November 2011
Accepted 8 November 2011
Available online 13 November 2011
ꢀ
ylation products using a catalytic amount of hydrazoneePd(OAc)
2
system with AgF at 60 C in good
yields.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Palladium catalyst
MizorokieHeck type reaction
Aryl trialkoxysilane
Hydrazone
1
. Introduction
R1
R1
N
N
N N
The arylation of olefines, also known as the MizorokieHeck
reaction, is one of the most widely used palladium-catalyzed
methodologies in organic synthesis. The efficiency of several cata-
lysts for the reaction of aryl halides with acrylates or styrene de-
rivatives has been studied. Mori reported a palladium-catalyzed
MizorokieHeck type reaction of olefines with aryl silanols instead
R2
R2
1
1
2
a: R , R = -(CH ) -
2
6
1
2
b: R , R = -(CH ) -
1
2 5
1
2
c: R , R = -(CH ) O(CH ) -
2
2
2 2
1
2
d: R = Ph, R = Me
2
of aryl halides. In this case, the reaction occurred using 10 mol % of
palladium catalyst at 100 C. On the other hand, Cheng recently
1
2
e: R = 2-pyridyl, R = Me
ꢀ
reported a palladium-catalyzed MizorokieHeck type reaction with
Fig. 1. Hydrazone ligands 1aee.
3
aryl trimethoxysilanes. Although this reaction occurred using
ꢀ
5
mol % of palladium catalyst at 60 C, a 10 mol % of ligand, such as
trialkoxysilanes using hydrazone ligand. n-Butyl acrylate (2a) and
phenyltrimethoxysilane (3a) were chosen as model substrates with
mol % of Pd catalyst for 24 h under an air atmosphere at 60 C
(Table 1). Using 10 mol % of hydrazone 1a as a ligand, we observed
that the MizorokieHeck type reaction in the presence of Pd(OAc)2
with AgF in DMF as a solvent proceeded to give corresponding
1,10-phenanthroline was used.
We recently demonstrated air-stable hydrazone as an effective
ꢀ
5
ligand for such palladium-catalyzed CeC bond formation as the
4
5
SuzukieMiyaura reaction, the MizorokieHeck reaction, the
6
Sonogashira cross-coupling reaction, the Hiyama cross-coupling
6a
reaction, and the allyl cross-coupling reaction of allylic acetate
with boronic acid.7 We now report the use of hydrazone ligands
product 4a in 70% yield (Table 1, entry 1). We tested other hydra-
zones 1bee and decreasing the amount of ligand (5 mol %) and
1
aee (Fig. 1) for a palladium-catalyzed MizorokieHeck type re-
8
found that hydrazone 1e (Fig. 2) was an effective ligand for this
action of olefines with aryl trialkoxysilanes.
reaction (entry 7). Without ligand, the reaction gave low yield of
the desired product (entry 8). When we used DMAc instead of DMF,
the yield increased to 79% (entry 9). We also investigated the effect
of various palladium sources and additives (entries 9e14). Using
2
. Results and discussion
Initially, we sought the optimal reaction conditions for a palla-
Pd(OAc)
When Ag
not occurred (entries 13 and 14). On the other hand, this reaction
proceeded with low yield using CuF (entry 15). Thus, we think that
2
with AgF led to good yield for this reaction (entry 9).
dium-catalyzed MizorokieHeck type reaction of olefines with aryl
2
CO and CsF were used instead of AgF, the reaction was
3
*
Corresponding author. Tel.: þ81 43 290 3385; fax: þ81 43 290 3401; e-mail
address: tmino@faculty.chiba-u.jp (T. Mino).
2
0
040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.11.027

430
T. Mino et al. / Tetrahedron 68 (2012) 429e432
Table 1
Table 2
Palladium-catalyzed MizorokieHeck reaction of olefins with aryl trialkoxysilanesa
Optimization of reaction conditions on the palladium-catalyzed MizorokieHeck
reaction of n-butyl acrylate with phenyltrimethoxysilane
a
Pd(OAc)
2
Pd source
O
ligand 1e, AgF
O
Si(OMe)3
ligand 1, additive
R
+
R
ArSi(OR')3
+
n
O Bu
Ar
n
O Bu
DMAc, 60 °C
solvent, 60 °C
2
4 h, Air
2
3 (R' = Me)
or
4
24 h, Air
2a
3a
4a
5 (R' = Et)
Yieldb (%)
Entry
R
R
0
Ar
Product
Yieldb (%)
Entry
Ligand
Pd source
Additive
Solvent
n
1
2
3
4
5
6
7
8
9
1a (10 mol %)
1b (10 mol %)
1c (10 mol %)
1d (10 mol %)
1e (10 mol %)
1a (5 mol %)
1e (5 mol %)
d
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
2
2
2
2
2
2
2
2
2
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
AgF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMAc
DMAc
DMAc
DMAc
DMAc
DMAc
DMAc
DMAc
NMP
70
42
56
55
70
60
76
49
79
60
37
41
0
1
2
3
4
COO Bu (2a)
Me
Me
Me
Et
Et
Et
Et
Et
Et
Me
Me
Me
Me
Me
Me
Ph (3a)
p-MeOC
p-MeC H (3c)
6 4
Ph (5a)
4a
4b
4c
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
84
81
60
75
55
64
89
83
16
70
80
73
34
75
45
n
COO Bu (2a)
6
H
4
(3b)
n
COO Bu (2a)
n
COO Bu (2a)
c
n
5
6
COO Bu (2a)
p-MeOC
6
H
4
(5b)
(5c)
(5d)
c
n
COO Bu (2a)
p-MeC
p-CF
p-ClC
6
H
4
n
7
8
9
10
11
COO Bu (2a)
3
C
6
H
4
n
COO Bu (2a)
6
H
4
(5e)
n
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
1e (5 mol %)
COO Bu (2a)
2-Thiophenyl (5f)
Ph (3a)
Ph (3a)
Ph (3a)
Ph (3a)
t
10
11
12
13
14
15
16
17
Pd(TFA)
PdCl
Pd (dba)
2
COO Bu (2b)
2
COOEt (2c)
COOMe (2d)
COMe (2e)
Ph (2f)
d
2
3
12
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
2
2
Ag CO
3
13
14
15
2
2
2
2
CsF
0
Ph (3a)
Ph (3a)
t
CuF
2
21
84
84
Bu (2g)
c
c
AgF
AgF
a
Reaction conditions: olefins (0.5 mmol), aryl trialkoxysilane (1.0 mmol), ligand
e (5 mol %), Pd(OAc)
ꢀ
1
2
(5 mol %), AgF (1.5 mmol), DMAc (1 mL) at 60 C for 24 h
a
Reaction conditions: n-butyl acrylate (0.5 mmol), phenyltrimethoxysilane
under air.
b
(
6
0.75 mmol), ligand 1, Pd source (5 mol %), additive (1.5 mmol), solvent (1 mL) at
Isolated yields.
This reaction was used NMP as a solvent.
This reaction was carried out at 50 C.
ꢀ
c
0
C for 24 h under air.
Isolated yields.
Phenyltrimethoxysilane (1.0 mmol) was used.
b
d
ꢀ
c
Fig. 2. The ORTEP drawing of 1e.
Ag(I) and Cu(II) act as oxidants of Pd(0) and fluoride ion activates
phenyltrimethoxysilane in this reaction. Using 2 equiv of phenyl-
trimethoxysilane (3a) led to high yield for this reaction (entry 16).
When we used NMP instead of DMAc, the reaction also proceeded
with high yield (entry 17).
3. Conclusion
We found that the MizorokieHeck type reaction of olefines with
aryl trialkoxysilanes gave corresponding products using a catalytic
amount of the hydrazoneePd(OAc)
ꢀ
2
system with AgF at 60 C in
Under optimized reaction conditions, the effect of various aryl
trialkoxysilanes in the MizorokieHeck type reaction was in-
vestigated using olefins (Table 2). Using aryl trimethoxysilanes
good yields.
4. Experimental section
4.1. General experimental
3aec led to good yields of the corresponding products (entries
1e3). Aryl triethoxysilanes 5aee also led to good yields (entries
4e8). Unfortunately, reactions with heteroaryl triethoxysilane,
such as 2-thiophenyltriethoxysilane (5f), gave corresponding
product 4f in low yield (entry 9). We also tested the reaction of
various olefins (entries 10e15). Using methyl acrylate led to good
1H NMR and 13C NMR spectra were measured with a Bruker
DPX-300 spectrometer (300 MHz for H NMR and 75 MHz for
1
13
C
NMR). The chemical shifts are expressed in parts per million
downfield from tetramethylsilane as an internal standard. The mass
spectra (MS) of the compounds were recorded using a Shimadzu
GCeMS-QP 5050 (EI-MS) spectrometer. The high-resolution mass
spectra (HRMS) of the compounds were recorded using a Thermo
Fisher Sci. Exactive (ESI-MS) spectrometer.
ꢀ
yields of the MizorokieHeck reaction product 4i at 50 C (entry 12).
On the other hand, the reaction with methyl vinyl ketone gave
product 4j with low yield (entry 13). Using styrene and 3,3-
dimethyl-1-butene also led to moderate to good yields of the cor-
responding products (entries 14 and 15).

T. Mino et al. / Tetrahedron 68 (2012) 429e432
431
4
.2. Preparation of hydrazone 1e
1637, 1592, 1493, 1409, 1316, 1206, 1175, 1084, 1012, 992, 823, 744,
1
4
99, 438; H NMR (CDCl
3
)
d
: 0.97 (t, J¼7.4 Hz, 3H), 1.37e1.50 (m,
A
solution of 1-methyl-1-(2-pyridyl)hydrazine (0.275 g,
2H), 1.64e1.74 (m, 2H), 4.21 (t, J¼6.7 Hz, 2H), 6.41 (d, J¼16.1 Hz,
2
.23 mmol) in MeOH (3 mL) was added to 40 wt % of glyoxal in
1H), 7.36 (d, J¼8.5 Hz, 2H), 7.46 (d, J¼8.5 Hz, 2H), 7.63 (d,
13
water (0.145 g, 1.0 mmol) at room temperature. The mixture was
stirred for 20 h at room temperature. The white solid precipitated
and was collected by filtration, washed with hexane, and dried
under reduced pressure: 0.204 g, 0.76 mmol, 76% as a white solid;
J¼16.0 Hz, 1H); C NMR (CDCl
3
) d: 13.7, 19.2, 30.7, 64.5, 118.9,
129.1, 129.2, 132.9, 136.1, 143.1, 166.8; EI-MS m/z (rel intensity) 238
þ
(M , 20).
ꢀ
ꢁ1
mp 218e219 C; IR (KBr, cm ): 3007, 2917, 1587, 1556, 1472, 1433,
360, 1312, 1288, 1200, 1155, 1121, 1044, 982, 965, 886, 857, 781,
4.3.6. (E)-n-Butyl 3-(2-thiophenyl)acrylate (4f). Yield 16% as
ꢁ
1
1
a brown oil; IR (neat, cm ): 2959, 2871, 1711, 1627, 1465, 1427,
1
1
766, 729, 688; H NMR (CDCl
3
)
d: 3.64 (s, 6H), 6.77e6.81 (ddd, J¼1.7,
1386, 1306, 1203, 1164, 1044, 970, 857, 705, 490, 407; H NMR
1
3
5
.0, and 6.3 Hz, 2H), 7.55e7.64 (m, 6H), 8.21e8.24 (m, 2H); C NMR
(CDCl
3
)
d
: 0.96 (t, J¼7.4 Hz, 3H), 1.37e1.49 (m, 2H), 1.63e1.73 (m,
(
CDCl
3
)
d
: 29.6, 109.7, 115.8, 135.0, 137.5, 147.0, 157.3; EI-MS m/z (rel
2H), 4.19 (t, J¼6.6 Hz, 2H), 6.24 (d, J¼15.7 Hz,1H), 7.04e7.07 (m,1H),
þ
13
intensity): 268 (M , 16); HRMS (ESI-MS) m/z calcd for C14
H
16
N
6
Na
7.25e7.27 (m, 1H), 7.38 (d, J¼5.1 Hz, 1H), 7.78 (d, J¼15.7 Hz, 1H);
NMR (CDCl : 13.7, 19.2, 30.7, 64.4, 117.0, 128.0, 128.3, 130.9, 137.0,
39.5, 167.0; EI-MS m/z (rel intensity) 210 (M , 29).
C
2
91.1329, found 291.1322.
3
) d
þ
1
4
.3. General procedure of palladium-catalyzed
MizorokieHeck type reaction with aryl trialkoxysilanes
4.3.7. (E)-tert-Butyl cinnamate (4g). Yield 70% as a colorless oil; IR
ꢁ
1
(
neat, cm ): 2978, 1708, 1637, 1449, 1367, 1329, 1150, 979, 871, 768,
1
To a mixture of olefin (0.5 mmol), AgF (0.191 mg, 1.5 mmol),
Pd(OAc) (5.6 mg, 25 mol), andligand 1e (6.7 mg, 25 mol) in DMAc
1.0 mL) was added aryl trialkoxysilane (1.0 mmol) at room temper-
3
685, 469, 447, 426, 411; H NMR (CDCl ) d: 1.54 (s, 9H), 6.37 (d,
2
m
m
J¼16.0 Hz, 1H), 7.36e7.38 (m, 3H), 7.49e7.53 (m, 2H), 7.59 (d,
13
(
J¼16.0 Hz, 1H); C NMR (CDCl
3
)
d
: 28.2, 80.5, 120.2, 127.9, 128.8,
ꢀ
þ
ature under an atmosphere of air. The mixture was stirred at 60 C.
After 24 h, the mixture was diluted with ethyl acetate and water. The
129.9, 134.7, 143.5, 166.3; EI-MS m/z (rel intensity) 204 (M , 10).
4
organic layer was washed with brine, dried over MgSO , and con-
centrated under reduced pressure. The residue was purified by silica
gel chromatography (hexane or hexane/EtOAc¼100 to 10/1).
4.3.8. (E)-Ethyl cinnamate (4h). Yield 80% as a colorless oil; IR
ꢁ
1
(neat, cm ): 1713, 1637, 1449, 1366, 1311, 1175, 1038, 980, 865, 768,
1
685, 480, 439, 418; H NMR (CDCl
3
)
d
: 1.34 (t, J¼7.1 Hz, 3H), 4.27 (q,
J¼7.1 Hz, 2H), 6.44 (d, J¼16.0 Hz, 1H), 7.36e7.39 (m, 3H), 7.51e7.54
13
4
.3.1. (E)-n-Butyl cinnamate (4a). Yield 84% as a colorless oil; IR
(m, 2H), 7.69 (d, J¼16.0 Hz, 1H); C NMR (CDCl
3
) d: 14.3, 60.5, 118.2,
ꢁ1
(
neat, cm ): 2957, 1712, 1637, 1450, 1309, 1170, 979, 767, 684, 478,
128.0, 128.8, 130.2, 134.4, 144.6, 167.0; EI-MS m/z (rel intensity) 176
1
þ
4
3
6
67, 453, 438, 425, 418, 412; H NMR (CDCl
3
)
d
: 0.97 (t, J¼7.4 Hz,
(M , 29).
H), 1.38e1.50 (m, 2H), 1.63e1.74 (m, 2H), 4.21 (t, J¼6.7 Hz, 2H),
.45 (d, J¼16.0 Hz, 1H), 7.36e7.39 (m, 3H), 7.51e7.55 (m, 2H), 7.69
4.3.9. (E)-Methyl cinnamate (4i). Yield 73% as a white solid; mp
1
3
ꢀ
ꢁ1
(
1
d, J¼16.0 Hz, 1H); C NMR (CDCl
3
)
d: 13.7, 19.2, 30.7, 64.4, 118.3,
33e34 C; IR (KBr, cm ): 2945, 1717, 1638, 1452, 1331, 1316, 1282,
1
28.0, 128.8, 130.2, 134.4, 144.5, 167.1; EI-MS m/z (rel intensity) 204
3
1203, 1172, 984, 773, 715, 688, 484; H NMR (CDCl ) d: 3.81 (s, 3H),
þ
(
M , 23).
6.45 (d, J¼16.0 Hz, 1H), 7.38e7.40 (m, 3H), 7.51e7.54 (m, 2H), 7.70
13
(
d, J¼16.0 Hz, 1H); C NMR (CDCl
3
)
d
: 51.7, 117.8, 128.1, 128.9, 130.3,
þ
4
.3.2. (E)-n-Butyl 3-(4-methoxyphenyl)acrylate (4b). Yield 81% as
134.4, 144.9, 167.4; EI-MS m/z (rel intensity) 162 (M , 49).
ꢁ1
a colorless oil; IR (neat, cm ): 2959, 1710, 1634, 1604, 1513, 1464,
1
1
(
2
422, 1311, 1288, 1253, 1169, 1031, 983, 828, 505, 444; H NMR
CDCl
: 0.96 (t, J¼7.3 Hz, 3H), 1.38e1.50 (m, 2H), 1.64e1.73 (m,
H), 3.84 (s, 3H), 4.20 (t, J¼6.6 Hz, 2H), 6.31 (d, J¼15.9 Hz, 1H), 6.90
4.3.10. (E)-4-Phenylbut-3-en-2-one (4j). Yield 34% as a yellow
ꢀ
ꢁ1
3
)
d
solid; mp 31e32 C; IR (KBr, cm ): 3027, 1667, 1609, 1576, 1496,
1
1450, 1359, 1329, 1257, 1204, 1182, 976, 750, 690, 498, 425;
NMR (CDCl
3H), 7.49e7.57 (m, 3H); C NMR (CDCl
H
13
(
d, J¼8.8 Hz, 2H), 7.48 (d, J¼8.8 Hz, 2H), 7.64 (d, J¼15.9 Hz, 1H);
C
3
)
d
: 2.39 (s, 3H), 6.72 (d, J¼16.3 Hz, 1H), 7.39e7.41 (m,
13
NMR (CDCl
3
)
d
: 13.7, 19.2, 30.8, 55.3, 64.2, 114.3, 115.7, 127.2, 129.7,
3
)
d
: 27.5, 127.1, 128.2,
þ
144.2, 161.3, 167.4; EI-MS m/z (rel intensity) 234 (M , 39).
128.9, 130.5, 134.4, 143.5, 198.4; EI-MS m/z (rel intensity) 146
þ
(
M , 69).
4
.3.3. (E)-n-Butyl 3-p-tolylacrylate (4c). Yield 64% as a colorless oil;
ꢁ1
IR (neat, cm ): 2959, 1714, 1637, 1608, 1514, 1457, 1310, 1278, 1204,
4.3.11. trans-Stilbene (4k). Yield 75% as
a
white solid; mp
1
ꢀ
ꢁ1
3
1169, 984, 814, 497, 445, 433, 423; H NMR (CDCl ) d: 0.96 (t,
124e125 C; IR (KBr, cm ): 3078, 3059, 3021, 1598, 1496, 1452,
1
J¼7.4 Hz, 3H),1.38e1.50 (m, 2H),1.64e1.74 (m, 2H), 2.37 (s, 3H) 4.20
1155, 1072, 984, 964, 909, 767, 693, 526; H NMR (CDCl
3
) d: 7.11 (s,
(
(
t, J¼6.7 Hz, 2H), 6.40 (d, J¼16.0 Hz, 1H), 7.19 (d, J¼8.0 Hz, 2H), 7.43
2H), 7.23e7.29 (m, 2H), 7.36 (t, J¼7.7 Hz, 4H), 7.52 (d, J¼7.1 Hz, 4H);
13
13
d, J¼8.1 Hz, 2H), 7.66 (d, J¼16.0 Hz, 1H); C NMR (CDCl
3
)
d: 13.7,
C NMR (CD
2 2
Cl ) d: 126.5, 127.7, 128.6, 128.7, 137.4; EI-MS m/z (rel
þ
1
9.2, 21.4, 30.8, 64.3, 117.1, 128.0, 129.6, 131.7, 140.6, 144.5, 167.3; EI-
intensity) 180 (M , 100).
þ
MS m/z (rel intensity) 218 (M , 32).
4
.3.12. trans-3,3-Dimethyl-1-phenyl-1-butene (4l). Yield 45% as
ꢁ
1
4
8
.3.4. (E)-n-Butyl 3-(4-trifluoromethylphenyl)acrylate (4d). Yield
a colorless oil; IR (neat, cm ): 3026, 2959, 2903, 2866, 1492, 1475,
1462, 1447,1361, 1265, 968, 745, 692; H NMR (CDCl
ꢁ1
1
9% as a colorless oil; IR (neat, cm ): 2962, 1716, 1644, 1577, 1416,
3
) d: 1.12 (s, 9H),
1
3
1324, 1173, 1067, 982, 833, 594, 499, 458, 446; H NMR (CDCl ) d:
6.25 (d, J¼16.2 Hz, 1H), 6.31 (d, J¼16.2 Hz, 1H), 7.18 (t, J¼7.2 Hz, 1H),
13
0
.97 (t, J¼7.3 Hz, 3H), 1.38e1.51 (m, 2H), 1.65e1.75 (m, 2H), 4.23 (t,
7.29 (t, J¼7.2 Hz, 2H), 7.36 (d, J¼7.1 Hz, 2H); C NMR (CDCl
3
) d: 29.6,
13
J¼6.7 Hz, 2H), 6.52 (d, J¼16.1 Hz, 1H), 7.61e7.72 (m, 5H); C NMR
CDCl
33.3, 124.6, 126.0, 126.7, 128.5, 138.1, 141.8; EI-MS m/z (rel intensity)
þ
(
3
)
d: 13.7, 19.2, 30.7, 64.7, 120.8, 123.8 (q, J¼272.0 Hz), 125.8 (q,
160 (M , 100).
J¼3.7 Hz), 128.1, 131.7 (q, J¼32.8 Hz), 137.9, 142.7, 166.5; EI-MS m/z
þ
(
rel intensity) 272 (M , 13).
Supplementary data
4
.3.5. (E)-n-Butyl 3-(4-chlorophenyl)acrylate (4e). Yield 83% as
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tet.2011.11.027.
ꢀ
ꢁ1
a white solid; mp 35e36 C; IR (KBr, cm ): 2963, 2867, 1706,

4
32
T. Mino et al. / Tetrahedron 68 (2012) 429e432
4. (a) Mino, T.; Shirae, Y.; Sakamoto, M.; Fujita, T. Synlett 2003, 882; (b) Mino, T.;
References and notes
Shirae, Y.; Sakamoto, M.; Fujita, T. J. Org. Chem. 2005, 70, 2191.
5
. (a) Mino, T.; Shirae, Y.; Sasai, Y.; Sakamoto, M.; Fujita, T. J. Org. Chem. 2006, 71,
1
. (a) de Meijere, A.; Meyer, F. Angew. Chem., Int. Ed. Engl. 1993, 33, 2379; (b)
Herrmann, W. A.; B o€ hm, V. P. W.; Reisinger, C.-P. J. Organomet. Chem. 1999, 576,
3; (c) Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009; (d) Whit-
combe, N. J.; Hii (Mimi), K. K.; Gibson, S. E. Tetrahedron 2001, 57, 7449; (e) Alonso,
F.; Beletskaya, I. P.; Yus, M. Tetrahedron 2005, 61, 11771.
6834; (b) Mino, T.; Shindo, H.; Kaneda, T.; Koizumi, T.; Kasashima, Y.; Sakamoto,
M.; Fujita, T. Tetrahedron Lett. 2009, 50, 5358.
. (a) Mino, T.; Shirae, Y.; Saito, T.; Sakamoto, M.; Fujita, T. J. Org. Chem. 2006, 71,
9
2
6
499; (b) Mino, T.; Suzuki, S.; Hirai, K.; Sakamoto, M.; Fujita, T. Synlett 2011, 1277.
. Mino, T.; Kajiwara, K.; Shirae, Y.; Sakamoto, M.; Fujita, T. Synlett 2008, 2711.
. CCDC number 840587. Empirical formula; C14
, M¼268.33, colorless pris-
7
8
2
. (a) Hirabayashi, K.; Nishihara, Y.; Mori, A.; Hiyama, T. Tetrahedron Lett. 1998, 39,
16 6
H N
7893; (b) Hirabayashi, K.; Ando, J.; Kawashima, J.; Nishihara, Y.; Mori, A.;
ꢀ
matic, monoclinic, space group, P21/c, a¼7.514(6), b¼5.106(4), c¼17.746(13) A,
Hiyama, T. Bull. Chem. Soc. Jpn. 2000, 73, 1409.
. Ye, Z.; Chen, F.; Luo, F.; Wang, W.; Lin, B.; Jia, X.; Cheng, J. Synlett 2009, 2198.
ꢀ
ꢀ
3
3
b
0
¼97.786(9) , V¼674.5(9) A , Z¼2, D
c
¼1.321 Mg/m , F(000)¼284,
m
(Mo K
a
)¼0.
3
ꢁ
1
86 mm .