Silylation and alkylation of allenes using chlorosilanes and alkyl halides in the presence of palladium catalyst and Grignard reagents

Article abstract of DOI:10.1016/j.jorganchem.2006.08.053

Allenes react with Grignard reagents and chlorosilanes in the presence of a palladium catalyst giving rise to carbosilylated products bearing carbon groups from Grignard reagents at the central carbon and silyl groups at the terminal carbon. When alkyl halides were used instead of chlorosilanes, the corresponding alkylated products were obtained.

Full text of DOI:10.1016/j.jorganchem.2006.08.053

Journal of Organometallic Chemistry 692 (2007) 375–381
www.elsevier.com/locate/jorganchem
Silylation and alkylation of allenes using chlorosilanes and alkyl
halides in the presence of palladium catalyst and Grignard reagents
*
Yuuki Fujii, Jun Terao , Hitoshi Kuniyasu, Nobuaki Kambe
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
Received 28 February 2006; accepted 6 July 2006
Available online 30 August 2006
Abstract
Allenes react with Grignard reagents and chlorosilanes in the presence of a palladium catalyst giving rise to carbosilylated products
bearing carbon groups from Grignard reagents at the central carbon and silyl groups at the terminal carbon. When alkyl halides were
used instead of chlorosilanes, the corresponding alkylated products were obtained.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Palladium catalyst; Allenes; Grignard reagent; Chlorosilanes; Alkyl halides
1. Introduction
(dba = dibenzylideneacetone) (0.03 mmol) at 25 °C under
nitrogen, and the resulting mixture was stirred for 1 h at
the same temperature. The NMR analysis of the crude
mixture indicated the formation of carbosilylated product
1 bearing phenyl group at the central carbon and triethyl-
silyl group at the terminal carbon in 92% yield and with
higher than 99% regio- and stereoselectivities (Eq. (1)).
The product was obtained in pure form in 67% yield by
column chromatography with hexane as the eluent. In this
reaction, only a trace amount of Et3SiPh (2%) was formed
as a byproduct, probably through the direct reaction of
Et3SiCl with PhMgBr. When PdCl2 was used instead of
Pd(dba)2, 1 was obtained in 71% yield. Under the same
conditions, palladium complexes bearing phosphine
ligands such as PdCl2(PPh3)2, Pd(PPh3)4 and NiCl2 were
ineffective.
Transition metal-catalyzed reactions which introduce
carbon and/or silyl functionalities to C–C unsaturated com-
pounds have been widely used for organic synthesis as use-
ful methods for construction of organic molecules. One of
our current projects is the regioselective silylation [1] and
alkylation [2] of alkenes and dienes using chlorosilanes
and alkyl halides by the combined use of transition metal
catalysts and Grignard reagents. During the course of this
study, we have found that Pd catalyzes silylation and alkyl-
ation of allenes using chlorosilanes and alkyl halides [3].
2. Results and discussions
2.1. Carbosilylation of arylallenes
A typical example is as follows. To a mixture of phen-
ylallene (1.0 mmol), Et3SiCl (1.3 mmol), and PhMgBr
(1.3 mmol) in THF (1.3 mL) was added Pd(dba)2
ð1Þ
*
Corresponding author.
E-mail addresses: terao@chem.eng.osaka-u.ac.jp (J. Terao), kambe@
chem.eng.osaka-u.ac.jp (N. Kambe).
0022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.08.053

376
Y. Fujii et al. / Journal of Organometallic Chemistry 692 (2007) 375–381
Some other representative results are shown in Table 1.
sponding coupling products 6 and 7 in 72% and 51% yield,
respectively (entries 5 and 6) although the stereoisomers
were obtained. a-Methyl and phenyl substituted phenylal-
lenes also underwent present coupling reaction (entries 7
and 8). The reaction was sluggish with respect to
alkylallenes.
This reaction also proceeded efficiently when Me3SiCl and
Ph2MeSiCl were used (entries 1 and 2). Chloro and
methoxy substituents on the aryl ring remained intact in
this reaction system (entries 3 and 4). The use of vinyl
and methyl Grignard reagents also afforded the corre-
Table 1
Pd-catalyzed carbosilylation of allenes with Grignard reagents and chlorosilanesa
Entry
1
Allene
R0-MgBr
Ph–MgBr
R030Si–Cl
Product
Yield (%)d
89
E/Ze
Me3Si–Cl
2
3
4
5
6
2/98
2
Ph2MeSi–Cl
82 (68)
90 (80)
87 (75)
(72)
2/98
1/99
1/99
30/70
3
p-Cl–C6H4–MgBr
Et3Si–Cl
4
p-OMe–C6H4–MgBr
Et3Si–Cl
5b
nPr3Si–Cl
6b
Me–MgBr
Ph–MgBr
nPr3Si–Cl
Et3Si–Cl
7
8
53 (51)
84 (72)
84/16
93/7
7c
8
Ph–MgBr
Et3Si–Cl
9
50 (38)
a
The reaction was carried out unless otherwise stated in THF at 25 °C for 1 h using arylallene (1.0 mmol), Grignard reagent (1.3 mmol), chlorosilane
(1.3 mmol), chlorosilane (1.3 mmol), and Pd(dba)2 (0.03 mmol).
b
Grignard reagent and chlorosilane were used in 1.5 mmol.
The reaction was carried out for 9 h.
NMR yield. Isolated yield is in parentheses.
Determined by GC.
c
d
e

Y. Fujii et al. / Journal of Organometallic Chemistry 692 (2007) 375–381
377
2.2. Hydrosilylation of arylallenes
When n-butyl Grignard reagent was used, expected
carbosilylated product 10a was obtained in 76% yield
along with 8% yield of hydrosilylated product 11 (Eq.
(2)). s-Butyl Grignard reagent gave nearly 1:1 mixture
of 10b and 11. Hydrosilylated product was predomi-
nantly obtained when t-butyl Grignard reagent was
employed. The yields of 11 increase in the order of
primary < secondary < tertiary reflecting the number of
b-hydrogens.
ð4Þ
2.4. Reaction mechanisms
Although the detailed mechanism of present coupling
reaction has not been clarified yet, plausible reaction path-
ways are shown in Scheme 1. The reaction of Pd(dba)2 with
arylallenes affords allene-palladium complexes 14 [6],
which reacts with Grignard reagents to give palladate com-
plexes 15 [7]. Direct reaction of palladate complexes 15
with chrolosilanes or alkyl halides at terminal or benzylic
carbon leads to palladium (II) complexes 16 (Path A).
The subsequent reductive coupling of these palladium (II)
complexes 16 gives silylated or alkylated products 17 and
regenerates Pd(0) to complete the catalytic cycle. Alterna-
tively, transmetallation of 14 with Grignard reagents via
15 gives carbomagnesation product 18, which is trapped
with chlorosilanes or alkyl halides to afford 17 (Path B).
Silyl groups are introduced regioselectively at the terminal
position of intermediates 15 or 18 due probably to the ste-
ric effect. When alkyl Grignard reagents are used, b-hydro-
gen elimination of 16 leading to hydrosilylation products
predominates over the reductive coupling to form 17.
In order to confirm the validity of the plausible reaction
pathways, we first tested the intermediary of carbomagne-
sation products 18, which may be formed by addition of
Grignard reagents toward allenes, since it is known that
transition metal catalyzes carbometalation of allenes with
organometallic reagents [8]. A reaction of phenylallene
with phenyl Grignard reagent was carried out in the pres-
ence of Pd(dba)2 under identical conditions to those of
ð2Þ
We carried out control experiments in order to
prove the hydrogen source for the formation of
11. When the reaction mixture of Eq. (2) using
t-BuMgCl was quenched with D2O before work-up,
deuterated 11 was not obtained at all. This result
would rule out the formation of silylmagnesation
intermediates.
Since it is known that a palladium complex catalyzes
hydrosilylation of allenes to give allylsilanes [4], we next
examined whether a similar hydrosilylation process is
involved in the present reaction. When a reaction similar
to that in entry 3 of Eq. (2) was carried out in the pres-
ence of nPr3SiCl and Et3SiH, only 12 having nPr3Si
group was obtained as silylated product and 84% of
Et3SiH was recovered (Eq. (3)). These results suggest
that hydrogen would be derived from alkyl group of
Grignard reagents.
ð3Þ
2.3. Arylalkylation of arylallenes
Use of 1-bromooctane instead of chlorosilanes yielded
three component coupling products 13a and 13b in 24%
and 51% yields, respectively (Eq. (4)). Under the same con-
ditions, 1-chlorooctane gave low yields of coupling prod-
ucts. It should be noted that the present reaction
proceeds efficiently in the case of alkyl fluorides with supe-
rior yields and regioselectivities compared with other
halides [5].
Scheme 1. Plausible pathways.

378
Y. Fujii et al. / Journal of Organometallic Chemistry 692 (2007) 375–381
Eq. (1). Quenching the reaction mixture with D2O gave a
30:70 mixture of arylated compounds (19a, 19b) which con-
tain a deuterium at an allylic position in 27% total yield
(Eq. (5)). When reaction mixture was treated with Et3SiCl
instead of D2O, 29% yield of carbosilylated product 1 was
obtained. These results suggest the formation of carbo-
magnesation product 18 (R = Ph) in the present reaction,
although Path B (18 ! 17) may not be the major pathway
due to the low yields of the trapped products.
more efficiently in the catalytic system than in Eq. (6). These
results would indicate that the palladate complexe 15 is the
active catalytic species and is more reactive than 18.
ð6Þ
ð7Þ
3. Conclusion
In conclusion, a new method for palladium catalyzed
silylation or alkylation of arylallenes has been developed.
This study provides the first example of a C–Si and C–C
bond forming reaction of allenes using chlorosilanes and
alkyl halides. Mechanistic details including the specific fea-
tures of the palladate complex are currently under
investigation.
ð5Þ
4. Experimental
1H NMR and 13C NMR spectra were recorded with a
JEOL JNM-Alice 400 (400 MHz and 100 MHz, respec-
tively) spectrometer. Chemical shifts are reported in parts
per million (d) downfield from internal tetramethylsilane.
Infrared spectra were recorded with a Perkin–Elmer FT-
IR (Model 1600). Both conventional and high resolution
mass spectra were recorded with a JEOL JMS-DX303HF
spectrometer. GC Mass spectra (EI) were obtained using
a JMS-mate operating in the electron impact mode
(70 eV) equipped with a RTX-5 30MX.25MMX.25U col-
umn. HPLC separations were performed on a recycling
preparative HPLC (Japan Analytical Industry Co. Ltd.,
Model LC-908) equipped with JAIGEL-1H and -2H col-
umns (GPC) using CHCl3 as an eluent. Column chroma-
tography was conducted using Kanto Chemical Co., Inc.
silica gel 60 (63–210lm). Elemental analyses were per-
formed on a Perkin–Elmer 240C apparatus. GC yields were
determined using decane as an internal standard. Grignard
reagents (Kanto Chemical Company), triethylchlorosilane,
triethylsilane (Shin-Etsu Chemical Company), trimethyl-
chlorosilane, tripropylchlorosilane, methyldiphenylchlo-
rosilane, octyl fluoride (Aldrich Chemical Company),
octyl chloride, octyl bromide, D2O (Wako Pure Chemical
Industries), Pd(dba)2 (Tokyo Chemical Industry Com-
pany) were purchased and used as received. Phenylallenes
were prepared according to the literature [9].
Next, we examined the time course of the Pd-catalyzed
reaction of phenylallene with phenyl Grignard reagent in
the absence (Eq. (6)) and presence (Eq. (7)) of Et3SiCl. Into
a mixture of phenylallene (0.5 mmol) and PhMgBr
(0.65 mmol) was added Pd(dba)2 (0.015 mmol) and the mix-
ture was stirred for 1, 3, 5, 7, 10 or 15 min. After trapping
the formed product with Et3SiCl at 25 °C for 1 min, the
reaction was quenched with 1 N HCl. The yield of 1 for
the reaction of Eq. (6) was plotted in Fig. 1 together
with the result of the catalytic reaction depicted in Eq. (7)
where the reaction was carried out in the presence of
Et3SiCl and quenched directly with 1 N HCl. The evidence
that the yield of 1 increases linearly indicates that the rate of
formation of 1 is independent on the concentration of sub-
strates and that the reductive elimination from 16 can be the
rate determining step if the reaction follows Path A. On the
other hand, forming rate of 1 in Eq. (6) decreased against
reaction time. At any stage of the reaction, 1 was formed
4.1. Typical procedure for palladium-catalyzed
carbosilylation of phenylallene using phenyl Grignard
reagent and triethylchlorosilane (Eq. (1))
To a mixture of phenylallene (114.5 mg, 0.985 mmol),
triethylchlorosilane (0.22 mL, 1.3 mmol) and Ph–MgBr
(1.0 M in THF, 1.3 mL, 1.3 mmol) was added Pd(dba)2
(17.3 mg, 0.03 mmol) at 25 °C under nitrogen. After
Fig. 1. Time course of the formation of 1 in Eqs. 6 and 7.

Y. Fujii et al. / Journal of Organometallic Chemistry 692 (2007) 375–381
379
stirring for 1 h, aqueous 1 N HCl was added and the prod-
ucts were extracted with ether. The organic layer was dried
over MgSO4 and evaporated to give yellow crude products
(92% yield according to NMR spectroscopy). Purification
by column chromatography on silica gel with hexane as
the eluent afforded 204 mg (67%) of 1.
J = 8.0 Hz, 6H); 13C NMR (100 MHz, CDCl3): 158.6,
140.9, 138.9, 137.5, 128.6, 128.0, 127.7, 125.7, 124.4,
113.3, 55.3, 16.9, 7.4, 4.1; MS (EI) m/z (relative intensity,
%): 338 (M+, 52), 310 (2), 309 (7), 137 (6), 117 (7), 116
(12), 115 (100), 88 (8), 87 (86), 59 (29); HRMS calcd for
C22H30OSi: 338.2066, found 338.2068.
4.2. Spectral data
4.2.5. (Z)-3-Methyl-1-phenyl-2-[(tripropylsilyl)methyl]-
1,3-butadiene (6)
4.2.1. (Z)-1,2-Diphenyl-3-triethylsilyl-1-propene (1)
IR (NaCl): 3055, 3022, 2952, 2874, 1598, 1494, 1456,
IR (NaCl): 3023, 2954, 2924, 2867, 1603, 1460, 1409,
1373, 1332, 1203, 1150, 1068, 1005, 888, 840, 743,
1
1446, 1414, 1237, 1156, 1004, 822 cmꢀ1
;
1H NMR
698 cmꢀ1; H NMR (400 MHz, CDCl3): d 7.34–7.14 (m,
(400 MHz, CDCl3): d 7.46–7.19 (m, 10H), 6.51 (s, 1H),
2.33 (s, 2H), 0.76 (t, J = 8.0 Hz, 9H), 0.34 (q, J = 8.0 Hz,
6H); 13C NMR (100 MHz, CDCl3): 145.1, 141.5, 138.7,
128.6, 128.0, 126.9, 126.7, 125.9, 125.52, 125.50, 17.0, 7.4,
4.1; MS (EI) m/z (relative intensity, %): 308 (M+, 38),
279 (6), 116 (11), 115 (100), 107 (6), 88 (7), 87 (70), 59
(22); HRMS calcd for C21H28Si: 308.1960, found
308.1965; Anal. Calc. for C21H28Si: C, 81.75; H, 9.15.
Found: C, 81.48; H, 9.21%.
5H), 6.50 (s, 1H), 5.12 (s, 1H), 5.04 (s, 1H), 2.07 (s, 2H),
2.03 (s, 3H), 1.21–1.11 (m, 6H), 0.86 (t, J = 7.2 Hz, 9H),
0.43–0.39 (m, 6H); NOE difference measurement: irradia-
tion of vinyl proton at d 6.50 caused 8.5% enhancement
of methyl protons at d 2.03, irradiation of methyl protons
at d 2.03 caused 5.2% enhancement of vinyl proton at d
6.50; 13C NMR (100 MHz, CDCl3): 145.2, 140.7, 139.1,
128.8, 127.9, 125.8, 124.0, 113.2, 21.8, 20.2, 18.8, 17.4,
16.2; MS (EI) m/z (relative intensity, %): 314 (M+, 26),
158 (11), 157 (84), 145 (8), 116 (14), 115 (100), 87 (21), 73
(38), 59 (11), 45 (16); HRMS calcd for C21H34Si:
314.2430, found 314.2437.
4.2.2. (Z)-3-Methyldiphenylsilyl-1,2-diphenyl-1-propene
(3)
IR (KBr): 3051, 3023, 2959, 1612, 1598, 1491, 1445,
1427, 1254, 1151, 1110, 989, 833, 789, 766, 735,
4.2.6. (E)-2-Methyl-1-phenyl-3-tripropylsilyl-1-propene (7)
IR(NaCl): 3022, 2954, 2925, 2868, 1640, 1493, 1454,
1409, 1374, 1333, 1202, 1158, 1068, 1008, 816, 743,
1
700 cmꢀ1; H NMR (400 MHz, CDCl3): d 7.53–7.09 (m,
20H), 6.57 (s, 1H), 2.84 (s, 2H), 0.23 (s, 3H); 13C NMR
(100 MHz, CDCl3): 144.2, 139.9, 138.2, 136.5, 134.3,
129.0, 128.5, 127.96, 127.95, 127.5, 127.0, 126.81, 126.75,
126.0, 19.5, ꢀ3.5; MS (EI) m/z (relative intensity, %): 390
(M+, 10), 199 (5), 198 (19), 197 (100), 181 (2), 165 (2),
119 (2), 105 (4); HRMS calcd for C28H26Si: 390.1804,
found 390.1801; Anal. Calc. for C28H26Si: C, 86.10; H,
6.71. Found: C, 85.81; H, 6.63%.
1
698 cmꢀ1; H NMR (400 MHz, CDCl3): d 7.30–7.12 (m,
5H), 6.13 (s, 1H), 1.87 (d, J = 1.2 Hz, 3H), 1.84 (d,
J = 0.8 Hz, 2H), 1.30–1.20 (m, 6H), 0.90 (t, J = 7.2 Hz,
9H), 0.52–0.48 (m, 6H); 13C NMR (100 MHz, CDCl3):
139.2, 137.7, 128.4, 127.9, 125.2, 122.6, 27.6, 19.7, 18.8,
17.5, 16.3; MS (EI) m/z (relative intensity, %): 288 (M+,
17), 245 (4), 161 (5), 159 (6), 158 (12), 157 (82), 116 (12),
115 (100), 87 (21), 73 (39), 59 (13), 45 (15); HRMS calcd
for C19H32Si: 288.2273, found 288.2283; Anal. Calc. for
C19H32Si: C, 79.09; H, 11.18. Found: C, 79.01; H, 11.26%.
4.2.3. (Z)-2-(4-Chlorophenyl)-1-phenyl-3-triethylsilyl-1-
propene (4)
IR (NaCl): 3055, 3024, 2953, 2874, 1618, 1598, 1494,
1456, 1414, 1237, 1156, 1093, 1014, 818, 747, 699 cmꢀ1
;
4.2.7. (E)-2,3-Diphenyl-1-triethylsilyl-2-butene (8)
IR (NaCl): 3055, 3019, 2952, 2874, 1599, 1489, 1442,
1H NMR (400 MHz, CDCl3): d 7.40–7.20 (m, 9H), 6.49
(s, 1H), 2.29 (s, 2H), 0.77 (t, J = 8.0 Hz, 9H), 0.34 (q,
J = 8.0 Hz, 6H); 13C NMR (100 MHz, CDCl3): 143.5,
140.3, 138.4, 132.6, 128.6, 128.12, 128.07, 127.9, 126.1,
126.0, 16.9, 7.4, 4.1; MS (EI) m/z (relative intensity, %):
342 (M+, 19), 313 (3), 117 (4), 116 (13), 115 (100), 88 (7),
87 (74), 59 (25); HRMS calcd for C21H27ClSi: 342.1571,
found 342.1568; Anal. Calc. for C21H27ClSi: C, 73.54; H,
7.93. Found: C, 73.47; H, 7.89%.
1414, 1236, 1159, 1017, 967, 762, 699 cmꢀ1 1H NMR
;
(400 MHz, CDCl3): d 7.06–6.91 (m, 10H), 2.13 (s, 3H),
2.10 (s, 2H), 0.82 (t, J = 0.8 Hz, 9H), 0.40 (t, J = 8.0 Hz,
6H); 13C NMR (100 MHz, CDCl3): 144.9, 144.3, 135.8,
129.7, 129.3, 129.2, 127.22, 127.16, 125.4, 125.0, 21.9,
21.7, 7.4, 4.2; MS (EI) m/z (relative intensity, %): 322
(M+, 29), 293 (7), 116 (12), 115 (100), 107 (5), 88 (8), 87
(78), 59 (26); HRMS calcd for C22H30Si: 322.2117, found:
322.2112; Anal. Calc. for C22H30Si: C, 81.92; H, 9.37.
Found: C, 81.92; H, 9.28%.
4.2.4. (Z)-2-(4-Methoxyphenyl)-1-phenyl-3-triethylsilyl-1-
propene (5)
IR (NaCl): 3021, 2952, 2874, 1607, 1510, 1464, 1415,
4.2.8. 3-Triethylsilyl-1,1,2-triphenyl-1-propene (9)
IR(KBr): 3053, 3020, 2950, 2873, 1598, 1492, 1442,
1285, 1247, 1179, 1038, 1004, 824, 749, 698 cmꢀ1
;
1H
NMR (400 MHz, CDCl3): d 7.39–7.34 (m, 6H), 7.22–7.16
(m, 1H), 6.88 (d, J = 8.4 Hz, 2H), 6.47 (s, 1H), 3.83 (s,
3H), 2.30 (s, 2H), 0.77 (t, J = 8.0 Hz, 9H), 0.35 (q,
1413, 1237, 1191, 1072, 1019, 762, 701 cmꢀ1 1H NMR
;
(400 MHz, CDCl3): d 7.35–6.88 (m, 15H), 2.04 (s, 2H),
0.77 (t, J = 8.0 Hz, 9H), 0.33 (q, J = 8.0 Hz, 6H); 13C

380
Y. Fujii et al. / Journal of Organometallic Chemistry 692 (2007) 375–381
NMR (100 MHz, CDCl3): 143.6, 143.5, 143.1, 138.6, 136.2,
130.6, 129.6, 129.5, 128.0, 127.4, 127.1, 126.1, 126.0, 125.2,
22.0, 7.5, 4.2; MS (EI) m/z (relative intensity, %): 384 (M+,
34), 355 (4), 191 (5), 116 (11), 115 (100), 107 (7), 91 (6), 88
(6), 87 (66), 59 (22); HRMS calcd for C27H32Si: 384.2273,
found: 384.2282.
C18H30Si: 274.2117, found: 274.2108; Anal. Calc. for
C18H30Si: C, 78.75; H, 11.02. Found: C, 78.58; H, 10.92%.
4.2.12. (E)-1,2-Diphenyl-1-undecene (13a)
IR (NaCl): 3053, 3021, 2954, 2854, 1598, 1494, 1465,
1443, 1074, 1029, 918, 759, 696 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 7.47–7.23 (m, 10H), 6.69 (s, 1H),
2.69 (t, J = 7.6 Hz, 2H), 1.45–1.38 (m, 2H), 1.28–1.21 (m,
12H), 0.87 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d 143.2, 142.9, 138.2, 128.6, 128.2, 128.1, 127.9,
126.9, 126.4, 126.3, 32.0, 30.3, 29.8, 29.6, 29.5, 29.4, 28.8,
22.8, 14.3; MS (EI) m/z (relative intensity, %): 306 (M+,
100), 194 (93), 193 (84), 179 (43), 178 (38), 129 (14), 117
(21), 116 (40), 115 (70), 103 (13), 91 (68); HRMS calcd
for C23H30: 306.2348, found: 306.2352.
4.2.9. (Z)-1-Phenyl-2-[(triethylsilyl)methyl]-1-hexene
(10a)
IR (NaCl): 3055, 3022, 2952, 2930, 2873, 1636, 1598,
1
1492, 1465, 1414, 1238, 1156, 1016, 750 cmꢀ1; H NMR
(400 MHz, CDCl3): d 7.30–7.22 (m, 4H), 7.15–7.12 (m,
1H), 6.12 (s, 1H), 2.11 (t, J = 7.2 Hz, 2H), 1.86 (s, 2H),
1.55–1.47 (m, 2H), 1.37 (qt, J = 7.2 Hz, 2H), 0.94 (t,
J = 7.2 Hz, 3H), 0.86 (t, J = 8.0 Hz, 9H), 0.51 (q,
J = 8.0 Hz, 6H); NOE difference measurement: irradiation
of vinyl proton at d 6.12 caused 5.4% enhancement of
methylene protons at d 2.11 (–CH2–nPr), irradiation of
methylene protons at d 2.11 (–CH2–nPr) caused 5.3%
enhancement of vinyl proton at d 6.12; 13C NMR
(100 MHz, CDCl3): d 141.7, 139.3, 128.5, 127.9, 125.2,
121.8, 40.1, 30.8, 22.7, 16.8, 14.3, 7.5, 4.4; MS (EI) m/z (rel-
ative intensity, %): 288 (M+, 16), 259 (4), 117 (4), 116 (11),
115 (100), 88 (6), 87 (68), 59 (19); HRMS calcd for
C19H32Si: 288.2273, found: 288.2277; Anal. Calc. for
C19H32Si: C, 79.09; H, 11.18. Found: C, 78.80; H, 11.03%.
4.2.13. 2,3-Diphenyl-1-undecene (13b)
IR (NaCl): 3080, 3023, 2924, 2852, 1626, 1600, 1493,
1451, 1074, 1028, 899, 777, 697 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 7.38–7.13 (m, 10H), 5.37 (s, 1H),
5.17 (s, 1H), 3.75 (t, J = 7.6 Hz, 1H), 1.93–1.85 (m, 1H),
1.81–1.73 (m, 1H), 1.43–1.22 (m, 12H), 0.86 (t,
J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d 151.7,
143.5, 142.5, 128.03, 127.95, 127.8, 126.9, 126.6, 125.9,
113,0 50.5, 35.3 32.0, 29.8, 29.6, 29.4, 28.1, 22.8, 14.3;
MS (EI) m/z (relative intensity, %): 306 (M+, 10), 195
(16), 194 (100), 193 (45), 179 (14), 178 (14), 117 (9), 115
(31), 105 (9), 103 (9), 91 (45); HRMS calcd for C23H30:
306.2348, found: 306.2343; Anal. Calc. for C23H30: C,
90.13; H, 9.87. Found: C, 89.88; H, 9.60%.
4.2.10. (Z)-3-Methyl-1-phenyl-2-[(triethylsilyl)methyl]-1-
pentene(10b)
IR (NaCl): 3056, 3022, 2956, 2874, 1636, 1598, 1494,
1460, 1415, 1377, 1238, 1154, 1017, 749, 698 cmꢀ1
;
1H
4.2.14. CAS registry numbers of other compounds known in
the literature
Compound 2, 221280-63-3 and Compound 11, 63522-
98-5.
NMR (400 MHz, CDCl3): d 7.30–7.22 (m, 4H), 7.14–7.11
(m, 1H), 6.09 (s, 1H), 2.01–1.91 (m, 2H), 1.78 (d,
J = 13.2 Hz, 1H), 1.68–1.58 (m, 1H), 1.46–1.35 (m, 1H),
1.12 (d, J = 6.8 Hz, 3H), 0.93 (t, J = 7.2 Hz, 3H), 0.85 (t,
J = 8.0 Hz, 9H), 0.85 (q, J = 8.0 Hz, 6H); NOE difference
measurement: irradiation of vinyl proton at d 6.09 caused
5.7% enhancement of methyl protons at d 1.12 (CH3-
CH), irradiation of methyl protons at d 1.12 (CH3-CH)
caused 2.7% enhancement of vinyl proton at d 6.09; 13C
NMR (100 MHz, CDCl3): 146.7, 139.5, 128.6, 127.8,
125.1, 119.5, 42.9, 29.3, 19.4, 17.7, 12.2, 7.5, 4.4; MS (EI)
m/z (relative intensity, %): 288 (M+, 16), 259 (4), 117 (4),
116 (11), 115 (100), 88 (6), 87 (65), 59 (19); HRMS calcd
for C19H32Si: 288.2273, found: 288.2280; Anal. Calcd for
C19H32Si: C, 79.09; H, 11.18. Found: C, 78.80; H, 11.15%.
Acknowledgements
This work was supported by Grant-in-Aid for Scientific
Research on Priority Areas (Nos. 15036241 and 16033237,
‘‘Reaction Control of Dynamic Complexes’’) from Minis-
try of Education, Culture, Sports, Science and Technology,
Japan and Industrial Technology Research Grant Program
in 2006 from New Energy and Industrial Technology
Development Organization (NEDO) of Japan.
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