Palladium-catalyzed allylation of aryl halides with homoallyl alcohols bearing a trisubstituted double bond: Application to chirality transfer from hydroxylated carbon to benzylic one

Article abstract of DOI:10.1021/jo100857d

(Figure presented) A facile route to homoallyl alcohols bearing a trisubstituted double bond has been devised. The palladium-catalyzed reactions of aryl halides with the alcohols thus synthesized result in regiospecific allyl transfer from the alcohols to aryl halides via retro-allylation, providing allylarenes having two substituents at the 1 and 2 positions of the allyl moiety. Optically active homoallyl alcohols transfer their chirality at the hydroxylated carbon to the benzylic carbon of the product.

Full text of DOI:10.1021/jo100857d

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Palladium-Catalyzed Allylation of Aryl Halides with Homoallyl Alcohols
Bearing a Trisubstituted Double Bond: Application to Chirality Transfer
from Hydroxylated Carbon to Benzylic One
Ryota Wakabayashi,† Daishi Fujino,†,‡ Sayuri Hayashi,† Hideki Yorimitsu,*,†,‡ and
Koichiro Oshima*,†
†Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku
Katsura, Nishikyo-ku, Kyoto 615-8510, Japan, and ‡Department of Chemistry, Graduate School of Science,
Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
yori@kuchem.kyoto-u.ac.jp; oshima@orgrxn.mbox.media.kyoto-u.ac.jp
Received April 30, 2010
A facile route to homoallyl alcohols bearing a trisubstituted double bond has been devised. The
palladium-catalyzed reactions of aryl halides with the alcohols thus synthesized result in regiospecific
allyl transfer from the alcohols to aryl halides via retro-allylation, providing allylarenes having two
substituents at the 1 and 2 positions of the allyl moiety. Optically active homoallyl alcohols transfer
their chirality at the hydroxylated carbon to the benzylic carbon of the product.
Introduction
allylarenes of interest. However, highly regio- and stereocon-
trolled allylation is difficult to achieve when substituted allylme-
tals such as crotylmetal are used.2,3 We have been developing the
use of homoallyl alcohols as allylmetal equivalents in the
palladium-catalyzed allylation of aryl halides (Scheme 1):4-6
after oxidative addition and halide-alkoxide exchange, retro-
allylation provides σ-allyl(aryl)palladium, which undergoes
rapid reductive elimination to yield the corresponding allylarene.
The allyl transfer is proposed to occur via palladium-medi-
ated retro-allylation that proceeds through a six-membered
chairlike transition state. Therefore, design and synthesis of
Allylarenes are a useful class of compounds in organic
chemistry, being converted to a wide variety of functionalized
alkylarenes.1 Palladium-catalyzed reaction of aryl halides with
allylmetals is likely to be an efficient method for the synthesis of
(1) For recent examples, see: (a) Ohmiya, H.; Makida, Y.; Li, D.; Tanabe,
M.; Sawamura, M. J. Am. Chem. Soc. 2010, 132, 879–889. (b) Ohta, T.;
Kataoka, Y.; Miyoshi, A.; Oe, Y.; Furukawa, I.; Ito, Y. J. Organomet. Chem.
2007, 692, 671–677. (c) Axet, M. R.; Castillon, S.; Claver, C. Inorg. Chim.
Acta 2006, 359, 2973–2979.
(2) (a) Godschalx, J.; Stille, J. K. Tetrahedron Lett. 1980, 21, 2599–2602.
(b) Takemura, S.; Hirayama, A.; Tokunaga, J.; Kawamura, F.; Inagaki, K.;
Hashimoto, K.; Nakata, M. Tetrahedron Lett. 1999, 40, 7501–7505. (c) Trost,
(4) (a) Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. J. Am. Chem.
Soc. 2006, 128, 2210–2211. (b) Iwasaki, M.; Hayashi, S.; Hirano, K.;
Yorimitsu, H.; Oshima, K. J. Am. Chem. Soc. 2007, 129, 4463–4469. (c)
Iwasaki, M.; Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. Tetrahe-
dron 2007, 63, 5200–5203. (d) Hayashi, S.; Hirano, K.; Yorimitsu, H.;
Oshima, K. J. Am. Chem. Soc. 2007, 129, 12650–12651. (e) Yorimitsu, H.;
Oshima, K. Bull. Chem. Soc. Jpn. 2009, 82, 778–792.
(5) Reviews for palladium-catalyzed C-C bond cleavage of tertiary
alcohols: (a) Muzart, J. Tetrahedron 2005, 61, 9423–9463. (b) Nishimura,
T.; Uemura, S. Synlett 2004, 201–216. (c) Satoh, T.; Miura, M. Top.
Organomet. Chem. 2005, 14, 1–20.
(6) Cross-coupling reactions of organic halides with tertiary alcohols via
β-carbon elimination: (a) Nakano, M; Satoh, T.; Miura, M. J. Org. Chem.
2006, 71, 8309–8311. (b) Terao, Y.; Wakui, H.; Satoh, T.; Miura, M.;
Nomura, M. J. Am. Chem. Soc. 2001, 123, 10407–10408. (c) Nishimura,
T.; Uemura, S. J. Am. Chem. Soc. 1999, 121, 11010–11011. (d) Larock, R. C.;
Reddy, C. K. Org. Lett. 2000, 2, 3325–3327. (e) Chow, H.-F.; Wan, C.-W.;
Low, K.-H.; Yeung, Y.-Y. J. Org. Chem. 2001, 66, 1910–1913.
ꢀ
B. M.; Keinan, E. Tetrahedron Lett. 1980, 21, 2595–2598. (d) Mendez, M.;
Echavarren, A. M. Eur. J. Org. Chem. 2002, 15–28. (e) Goliaszewski, A.;
Schwartz, J. Tetrahedron 1985, 41, 5779–5789. (f) Lee, P. H.; Sung, S.-Y.;
Lee, K. Org. Lett. 2001, 3, 3201–3204. (g) Lee, K.; Lee, J.; Lee, P. H. J. Org.
Chem. 2002, 67, 8265–8268.
(3) Examples of selective allylation: (a) Obora, Y.; Tsuji, Y.; Kobayashi,
M.; Kawamura, T. J. Org. Chem. 1995, 60, 4647–4649. (b) Hatanaka, Y.;
Ebina, Y.; Hiyama, T. J. Am. Chem. Soc. 1991, 113, 7075–7076. (c)
Hatanaka, Y.; Goda, K.; Hiyama, T. Tetrahedron Lett. 1994, 35, 1279–
1282. (d) Hatanaka, Y.; Goda, K.; Hiyama, T. Tetrahedron Lett. 1994, 35,
6511–6514. (e) Hiyama, T.; Matsuhashi, H.; Fujita, A.; Tanaka, M.;
Hirabayashi, K.; Shimizu, M.; Mori, A. Organometallics 1996, 15, 5762–
5765. (f) Hiyama, T.; Hatanaka, Y. Pure Appl. Chem. 1994, 66, 1471–1478.
(g) Yamamoto, Y.; Takada, S.; Miyaura, N. Chem. Lett. 2006, 35, 704–705.
(h) Yamamoto, Y.; Takada, S.; Miyaura, N. Chem. Lett. 2006, 35, 1368–
1369. (i) Yamamoto, Y.; Takada, S.; Miyaura, N.; Iyama, T.; Tachikawa, H.
Organometallics 2009, 28, 152–160.
DOI: 10.1021/jo100857d
r
Published on Web 06/15/2010
J. Org. Chem. 2010, 75, 4337–4343 4337
2010 American Chemical Society

Wakabayashi et al.
JOCFeatured Article
SCHEME 1. Reaction Mechanism of Palladium-Catalyzed
Allylation of Aryl Halides with Homoallyl Alcohols
SCHEME 2. Representative Scheme for Synthesis of Homoallyl
Alcohols Bearing a Trisubstituted Double Bond
proper homoallyl alcohols are quite important to introduce
the needed allylic moieties.
Although we have prepared several homoallyl alcohols for the
palladium-catalyzed allylation, homoallyl alcohols 1 are the only
alcohols that bear a trisubstituted double bond (Figure 1).7
TABLE 1. Scope of Aryl Halidesa
entry
X
R
6
yield/%
1
2
3
4
5
6
Br
Cl
Br
Br
Br
Cl
Br
Br
Br
Br
I
H
H
4-Me
4-OMe
4-CF3
4-CO2Et
4-CHO
6a
6a
6b
6c
6d
6e
6f
6g
6h
6i
80
74
68
67
76
89
74
81
76
77
86
FIGURE 1. Hitherto known substitution patterns.
Unfortunately, the palladium-catalyzed allylation with 1 pro-
ceeded without regio- and stereospecificity because the electron-
withdrawing nature of the cyano group retarded reductive elimi-
nation that is responsible for regio- and stereospecific allylation
(eq 1). Hence, there are no examples of regio- and stereospecific
allylation with homoallyl alcohols bearing a trisubstituted double
bond. In addition, such highly substituted homoallyl alcohols
are difficult to synthesize in a stereoselective manner. To expand
the scope of homoallyl alcohols, we designed and prepared
homoallyl alcohols 2 (Scheme 2) and employed 2 in palladium-
catalyzed allylation of aryl halides, which we report herein.
7b
8b
9b
10
11
4-COPh
4-CN
(1-naphthyl)c
(3-pyridyl)d
6j
aConditions: 2e (0.40 mmol), aryl halide (1.5 equiv), Pd(OAc)2 (5 mol
%), P(cC6H11)3 (20 mol %), Cs2CO3 (1.5 equiv). bPPh3 was used instead
of P(cC6H11)3. c1-Bromonaphthalene was used as substrate. d3-Iodo-
pyridine was used as substrate.
After dimethylsilylation of 3, platinum-catalyzed intramole-
cular hydrosilylation of 48 yielded oxasilacyclopentane 5.
Since 5 partially decomposed during silica gel column puri-
fication, the crude oil containing 5 was directly treated with
organolithium to furnish silyl-substituted homoallyl alcohol
2a and 2b. Cross-coupling methylation and phenylation of 59
provided another type of homoallyl alcohols 2c and 2d,
respectively. Each step was easy to perform and high-yield-
ing. We prepared several additional homoallyl alcohols 2e-g
(Tables 1 and 2) according to this procedure.
Allylation Reaction. Treatment of bromobenzene with 2e in
the presence of cesium carbonate under Pd(OAc)2/P(cC6H11)3
catalysis in refluxing toluene provided the corresponding allyl-
benzene in 80% yield (Table 1, entry 1). The reaction proceeded
Results and Discussion
Synthesis of Homoallyl Alcohols. Homoallyl alcohols 2
were readily prepared as demonstrated in Scheme 2. Nucleo-
philic ring-opening reaction of R-methylstyrene oxide with
lithium acetylide afforded tertiary homopropargyl alcohol 3.
(8) Tamao, K.; Maeda, K.; Tanaka, T.; Ito, Y. Tetrahedron Lett. 1988, 29,
6955–6956.
(9) (a) Denmark, S. E.; Wehrli, D. Org. Lett. 2000, 2, 565–568. (b)
Denmark, S. E.; Weitao, P. Org. Lett. 2001, 3, 61–64. (c) Hatanaka, Y.;
Hiyama, T. Synlett 1991, 845–853. (d) Takahashi, K.; Minami, T.; Ohara, Y.;
Hiyama, T. Bull. Chem. Soc. Jpn. 1995, 68, 2649–2656.
(7) Ohmura, T.; Awano, T.; Suginome, M.; Yorimitsu, H.; Oshima, K.
Synlett 2008, 423–427.
4338 J. Org. Chem. Vol. 75, No. 13, 2010

Wakabayashi et al.
JOCFeatured Article
SCHEME 3. Chirality Transfer from (S)-2b and (S)-2f
TABLE 2. Scope of Homoallyl Alcoholsa
entry
R1
R2
2
R
6
yield/%
1
2
3
4b
5
6
7
8
nBu
nBu
nBu
nBu
nBu
nBu
SiMe3
SiMe3
SiMe3
SiMe2Ph
Me
Ph
SiMe3
SiMe3
2a
2a
2a
2b
2c
2d
2f
H
6a
6c
6e
6k
6l
6m
6n
6o
75
74
87
77
83
73
71
35c
MeO
CO2Et
H
H
H
TIPSOCH2
tBu
H
H
2g
aConditions: 2 (0.40 mmol), 4-RC6H4Br (1.5 equiv), Pd(OAc)2 (5 mol
%), P(cC6H11)3 (20 mol %), Cs2CO3 (1.5 equiv). bPPh3 was used instead
of P(cC6H11)3. cThe phenyl ether of 2g was obtained as a byproduct in
22% yield.
with optically pure (S)-2f, higher levels of chirality transfer
were observed.13,14
with perfect regioselectivity, and no 2-trimethylsilyl-2-hepte-
nylbenzene was detected. Chlorobenzene as well as electron-
rich 4-bromoanisole reacted smoothly without suffering from
slow oxidative addition (entries 2 and 4). Trifluoromethyl and
ethoxycarbonyl groups had little effect on the reaction (entries 5
and 6). Aryl bromides bearing the more electron-withdrawing
formyl, benzoyl, or cyano group were allylated by using PPh3 as
the ligand (entries 7-9).10 Sterically demanding 1-bromo-
naphthalene participated in the reaction (entry 10). A nitrogen-
containing heterocycle could be allylated (entry 11).
The high levels of chirality transfer from (S)-2f are rationa-
lized as follows (Scheme 4). Between two possible chairlike
transition states, 11a and 11b, of the retro-allylation, 11b would
be more favorable because 11a would suffer from the stronger
1,3-diaxial repulsion between the phenyl and silyl groups. The
palladium center would approach the Si(sinister)-face of the
alkene moiety, which results in the formation of 12 with S
configuration. Rapid reductive elimination from 12 without loss
of the chirality provides (R)-6k and (S)-6p-r.
The scope of homoallyl alcohols was examined (Table 2).
Compared to 2e, the increased steric hindrance around the
hydroxylated carbons of 2a-d and 2f led to a prolonged
reaction time, although the yields of the products were
satisfactory (entries 1-7). Instead of the trimethylsilyl group
of 2a, dimethylphenylsilyl, methyl, and phenyl groups on the
internal olefinic carbons were also compatible (entries 4-6).
Under the reaction conditions, the triisopropylsilyl ether of
2f survived (entry 7). Unfortunately, the tert-butyl group of
2g retarded the retro-allylation process (entry 8). Palladium-
catalyzed phenylation of the hydroxy group11 competed to
yield the phenyl ether of 2g as a byproduct.
SCHEME 4. Mechanism of Chirality Transfer
Previously, we reported successful chirality transfer from
an optically active homoallyl alcohol to allylarenes, in which
the alcohol having chirality at the allylic position was used
(eq 2, Np=1-naphthyl).4d However, a number of attempts to
transfer chirality from hydroxylated carbons failed, and we
observed only 19% ee at a maximum (eq 3). We were pleased
to find that optically enriched alcohol (S)-2b with a trisub-
stituted double bond realized satisfactory chirality transfer
from the hydroxylated carbon (Scheme 3).12 In the reaction
(10) The use of P(c-C6H11)3 resulted in conversion as low as 10%,
probably because of deactivation of the palladium catalyst.
(11) Buchwald, A. V.; Huang, X.; Buchwald, S. L. J. Am. Chem. Soc.
2005, 127, 8146–8149 and references cited therein.
Conclusion
(12) Because direct determination of the enantiomeric excess of 6k by
chiral HPLC was difficult, 6k was converted to 6m according to the literature:
Anderson, J. C.; Munday, R. H. J. Org. Chem. 2004, 69, 8971–8974. The
enantiomeric excess of 6m thus obtained was determined by chiral HPLC.
See the Supporting Information.
We have developed an easy route to homoallyl alcohols
bearing a trisubstituted double bond, taking advantage of
(13) Because determination of the enantiomeric excess of 6p-r was
difficult, the TIPS group was removed by tetrabutylammonium fluoride to
yield the corresponding chiral alcohols that were suitable for determination
of enantiomeric excess. See the Supporting Information.
(14) The absolute stereochemistry of (S)-6r was determined by X-ray
crystallographic analysis of the corresponding alcohol after desilylation. The
absolute stereochemistry of the other products was tentatively assigned. See
the Supporting Information.
J. Org. Chem. Vol. 75, No. 13, 2010 4339

Wakabayashi et al.
JOCFeatured Article
intramolecular hydrosilylation. The homoallyl alcohols thus
synthesized undergo palladium-catalyzed regioselective allyl
transfer to aryl halides via retro-allylation. The silyl substit-
uents at the more substituted olefinic carbon realize high
levels of chirality transfer from the hydroxylated carbon to
the benzylic carbon of the product.
0.50 M toluene solution) was charged in the reaction flask.
Toluene (0.40 mL), homoallyl alcohol 2e (91 mg, 0.40 mmol),
and bromobenzene (94 mg, 0.60 mmol) were sequentially added
at ambient temperature. The resulting mixture was heated at
reflux for 12 h. After the mixture was cooled to room tempera-
ture, water (20 mL) was added. The product was extracted with
hexane (20 mL Â 3). The combined organic layer was dried over
sodium sulfate and concentrated in vacuo. Silica gel column
purification with hexane as an eluent gave 6a (79 mg, 0.32 mmol)
in 80% yield.
Experimental Section
Preparation of Homoallyl Alcohols 2 (Scheme 2). A 100-mL
reaction flask was filled with argon. THF (7.4 mL), 1-hexyne
(1.70 mL, 14.8 mmol), and n-butyllithium (1.62 M hexane solu-
tion, 9.14 mL, 14.8 mmol) were added at 0 °C. The resulting mix-
ture was stirred for 30 min. Hexamethylphosphoramide (1.29
mL, 7.4 mmol) and R-methylstyrene oxide (0.99 g, 7.4 mmol)
were added at 0 °C. The mixture was allowed to warm to 40 °C
and stirred for 22 h at ambient temperature. After an addition of
a saturated ammonium chloride solution (20 mL), extraction,
evaporation, and purification on silica gel furnished propargyl
alcohol 3 (1.44 g, 6.67 mmol, 90%).
Alcohol 3 (1.44 g, 6.67 mmol) in THF (13 mL) was placed in a
50-mL reaction flask under argon. n-Butyllithium (1.62 M hexane
solution, 4.8 mL, 7.7 mmol) was added at 0 °C. After the mixture
was stirred for 30 min, chlorodimethylsilane (0.97 mL, 8.7 mmol)
was added. The resulting mixture was allowed to warm to room
temperature and was stirred for 8 h. Hexane (20 mL) was added,
and the resulting suspension was filtered through a pad of Celite.
The filtrate was concentrated in vacuo. Purification on silica gel
(Kanto Chemical, neutral) by using hexane/ethyl acetate = 20:1 as
an eluent provided silyl ether 4 (1.38 g, 5.03 mmol, 75%), along
with 3 recovered (0.31 g, 1.4 mmol).
Characterization Data. (E)-2-Phenyl-4-trimethylsilyl-4-nonen-
2-ol (2a): IR (neat) 3472, 2955, 2862, 1605, 1450, 1250, 1065, 841,
756, 702 cm-1; 1H NMR (CDCl3) δ 0.01 (s, 9H), 0.86-0.90 (m,
3H), 1.21-1.34 (m, 4H), 1.55 (s, 3H), 1.88 (s, 1H), 1.96-2.07 (m,
2H), 2.65 (d, J = 13.5 Hz, 1H), 2.72 (d, J = 13.5 Hz, 1H), 6.02 (t,
J =7.0 Hz, 1H), 7.24 (tt, J =7.0, 2.0Hz, 1H), 7.32-7.36 (m,2H),
7.46-7.49 (m, 2H); 13C NMR (CDCl3) δ 0.0, 14.2, 22.7, 29.5,
30.4, 31.8, 44.1, 74.9, 125.1, 126.7, 128.2, 136.7, 147.3, 149.3;
HRMS (FAB) found 289.1983 (M-H), calcd for C18H29OSi
289.1988.
(E)-4-Dimethylphenylsilyl-2-phenyl-4-nonen-2-ol (2b): IR
(neat) 3564, 3464, 2955, 2862, 1605, 1450, 1373, 1250, 1111,
1057, 818, 772, 702 cm-1; 1H NMR (CDCl3) δ 0.29 (s, 3H), 0.34
(s, 3H), 0.88 (t, J = 7.0 Hz, 3H), 1.22-1.34 (m, 4H), 1.41 (s, 3H),
1.59 (s, 1H), 1.99-2.08 (m, 2H), 2.61 (d, J = 14.0 Hz, 1H), 2.73
(d, J = 14.0 Hz, 1H), 6.12 (t, J = 7.0 Hz, 1H), 7.20 (tt, J = 7.5,
2.0 Hz, 1H), 7.26-7.30 (m, 2H), 7.32-7.37 (m, 5H), 7.49-7.53
(m, 2H); 13C NMR (CDCl3) δ -1.6, -1.4, 14.2, 22.7, 29.6, 30.0,
31.7, 44.3, 75.1, 125.0, 126.6, 128.0, 128.2, 129.0, 134.4, 134.7,
139.9, 149.07, 149.10. Anal. Calcd for C23H32OSi: C, 78.35; H,
9.15. Found: C, 78.54; H, 9.05.
(Z)-4-Methyl-2-phenyl-4-nonen-2-ol (2c): IR (neat) 3464,
2924, 2862, 1450, 1373, 1095, 1034, 941, 872, 764, 702 cm-1
;
H2PtCl6 6H2O (13 mg, 0.025 mmol) was placed in a 50-mL
3
1H NMR (CDCl3) δ 0.89 (t, J = 7.0 Hz, 3H), 1.22-1.34 (m, 4H),
1.40 (q, J = 1.5 Hz, 3H), 1.58 (s, 3H), 1.97-2.01 (m, 2H), 2.09 (s,
1H), 2.52 (d, J = 13.5 Hz, 1H), 2.68 (d, J = 13.5 Hz, 1H),
5.33-5.36 (m, 1H), 7.22 (tt, J = 7.5, 2.0 Hz, 1H), 7.31-7.34 (m,
2H), 7.45-7.47 (m, 2H); 13C NMR (CDCl3) δ 14.2, 22.6, 25.8,
28.5, 30.9, 32.3, 46.6, 74.6, 125.0, 126.7, 128.3, 131.3, 131.4,
148.9. HRMS (DART) found 231.1745(M - H), calcd for
C16H23O 231.1749.
reaction flask under argon. Silyl ether 4 (1.38 g, 5.03 mmol) was
diluted in dichloromethane (10 mL), and the solution was added to
the platinum catalyst. After the mixture was stirred for 1 h, the
solvent was removed in vacuo. The crude oxasilacyclopentane 5was
diluted in ether (10 mL) in a 50-mL reaction flask under argon.
Phenyllithium (1.15 M in hexane/ether, 6.6 mL, 7.5 mmol) was
added at -78 °C. After the mixture was stirred for 1 h, saturated
ammonium chloride solution (20 mL) was added at room tempera-
ture. Extraction, evaporation, and purification on silica gel (hexane/
ethyl acetate =40:1) furnished 2b (1.34 g, 3.81 mmol, 76%).
In a similar fashion, addition of methyllithium (1.09 M in
ether, 6.75 mL, 7.35 mmol) to crude 5 (from 4.9 mmol of 4)
afforded 2a (1.03 g, 3.54 mmol, 72%).
(E)-2,4-Diphenyl-4-nonen-2-ol (2d): IR (neat) 3456, 3024,
2963, 2924, 2862, 2739, 1597, 1497, 1450, 1373, 1103, 1065,
910, 864, 756, 694 cm-1; 1H NMR (CDCl3) δ 0.87-0.90 (t, J =
7.0 Hz, 3H), 1.26-1.33 (m, 4H), 1.42 (s, 3H), 1.83 (s, 1H),
2.02-2.06 (m, 2H), 3.05 (s, 2H), 5.68 (t, J = 7.0 Hz, 1H),
The procedure for the synthesis of 2d is as follows. Crude 5
(from 7.03 mmol of 4) was placed in a 50-mL reaction flask.
Tetrabutylammonium fluoride in THF (1.0 M, 14.1 mL, 14.1
mmol), iodobenzene (0.87 mL, 7.7 mmol), and Pd2(dba)3 (0.160
g, 0.175 mmol) were sequentially added. The mixture was stirred
at room temperature for 30 min. Extractive workup followed
by silica gel column purification (hexane/ethyl acetate = 10:1)
afforded 2d (1.64 g, 5.58 mmol, 79%).
Alcohol 2c was prepared in a similar fashion by using
iodomethane. It is worth noting that the order of charging
iodomethane and Pd2(dba)3 is important: after an addition of
tetrabutylammonium fluoride, Pd2(dba)3 was added first. Iodo-
methane was then added. Otherwise, the reaction gave signifi-
cant amounts of byproducts.
Reaction of Aryl Halides with Homoallyl Alcohols. Synthesis
of 6a (Table 1, entry 1) is representative. Cesium carbonate
(0.20 g, 0.60 mmol) was placed in a 20-mL two-necked reaction
flask equipped with a Dimroth condenser. The cesium carbo-
nate was dried in vacuo with heating with a hair dryer for 2 min.
Palladium acetate (4.5 mg, 0.020 mmol) was added. The flask
was then filled with argon by using the standard Schlenk
technique. Tricyclohexylphosphine (0.16 mL, 0.080 mmol,
7.16-7.28 (m, 2H), 7.25-7.28 (m, 6H), 7.37-7.40 (m, 2H); 13
C
NMR (CDCl3) δ 14.2, 22. 7, 29.1, 30.0, 32.0, 44.2, 75.6, 125.0,
126.6, 126.9, 127.0, 128.1, 128.6, 135.1, 136.2, 144.9, 148.3.
HRMS (FAB) found 293.1908 (M - H), calcd for C21H25O
293.1905.
(E)-2-Methyl-4-trimethylsilyl-4-nonen-2-ol (2e): IR (neat)
3472, 2963, 1605, 1466, 1373, 1250, 1126, 1057, 903, 841, 756,
687 cm-1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.89 (t, J = 7.5 Hz,
3H), 1.20 (s, 6H), 1.23-1.37 (m, 5H), 2.13 (dt, J = 7.5 Hz, 2H),
2.37 (s, 2H), 5.99 (t, J = 7.0 Hz, 1H); 13C NMR (CDCl3) δ 0.2,
14.3, 22.7, 29.6, 30.3, 31.9, 42.8, 71.9, 137.4, 146.1. Anal. Calcd
for C13H28OSi: C, 68.35; H, 12.35. Found: C, 68.24; H, 12.09.
(E)-2-Phenyl-6-triisopropylsiloxy-4-trimethylsilyl-4-hexen-2-
ol (2f): IR (neat) 3456, 2947, 2870, 1605, 1466, 1373, 1250, 1065,
1
1011, 841, 764, 687 cm-1; H NMR (CDCl3) δ 0.03 (s, 9H),
1.03-1.05 (m, 21H), 1.55 (s, 3H), 2.30 (s, 1H), 2.64 (d, J = 4.0 Hz,
2H), 3.87 (dd, J = 14.0, 6.0 Hz, 1H), 4.07 (dd, J = 14.0, 6.0 Hz,
1H), 6.11 (t, J = 6.0 Hz, 1H), 7.22 (tt, J = 7.5, 1.0 Hz, 1H), 7.32
(tt, J = 7.5, 1.0 Hz, 2H), 7.41-7.43 (m, 2H); 13C NMR (CDCl3)
δ -0.3, 12.2, 18.2, 30.6, 44.8, 60.9, 74.8, 125.2, 126.8, 128.3, 138.2,
145.7, 148.9. Anal. Calcd for C24H44O2Si2: C, 68.51; H, 10.54.
Found: C, 68.24; H, 10.53.
4340 J. Org. Chem. Vol. 75, No. 13, 2010

Wakabayashi et al.
JOCFeatured Article
(E)-6,6-Dimethyl-2-phenyl-4-trimethylsilyl-4-hepten-2-ol (2g):
IR (neat) 3472, 2955, 1597, 1450, 1366, 1250, 1049, 841, 756, 702
cm-1; 1H NMR (CDCl3) δ 0.00 (s, 9H), 1.13 (s, 9H), 1.54 (s, 3H),
1.86 (s, 1H), 2.69 (d, J = 13.5 Hz, 1H), 3.05 (d, J = 13.5 Hz, 1H),
5.93 (t, J = 7.0 Hz, 1H), 7.21-7.25 (m, 1H), 7.32-7.36 (m, 2H),
7.47-7.49 (m, 2H); 13C NMR (CDCl3) δ 0.6, 30.4, 31.6, 36.3,
43.0, 73.8, 125.0, 126.7, 128.3, 134.4, 150.0, 155.6; HRMS
(FAB) found 289.1975 (M - H), calcd for C18H29OSi 289.1988.
1.0 Hz, 1H), 5.76 (dd, J = 2.0, 1.5 Hz, 1H), 7.22-7.24 (m, 2H),
7.93-7.96 (m, 2H); 13C NMR (CDCl3) δ -0.9, 14.2, 14.6, 22.9,
30.3, 34.8, 50.4, 61.0, 124.3, 128.5, 128.6, 129.6, 150.1, 154.5,
166.9. Anal. Calcd for C19H30O2Si: C, 71.64; H, 9.49. Found: C,
71.91; H, 9.30.
4-(2-Trimethylsilyl-1-hepten-3-yl)benzaldehyde (6f): IR (neat)
2955, 2862, 2731, 1705, 1604, 1420, 1250, 1211, 1165, 934, 841,
756 cm-1; 1H NMR (CDCl3) δ -0.09 (s, 9H), 0.85 (t, J = 7.5 Hz,
3H), 1.08-1.16 (m, 1H), 1.19-1.34 (m, 3H), 1.67-1.74 (m, 1H),
1.81-1.88 (m, 1H), 3.50 (t, J = 7.5 Hz, 1H), 5.57 (dd, J = 2.0,
0.5 Hz, 1H), 5.77 (dd, J = 2.0, 1.5 Hz, 1H), 7.34 (d, J = 8.5 Hz,
2H), 7.79 (d, J = 8.5 Hz, 2H), 9.97 (s, 1H); 13C NMR (CDCl3) δ
-0.9, 14.2, 22.9, 30.3, 34.8, 50.6, 124.6, 129.3, 129.9, 134.9,
152.3, 154.2, 192.3. Anal. Calcd for C17H26OSi: C, 74.39; H,
9.55. Found: C, 74.60; H, 9.42.
Phenyl 4-(trimethylsilyl-1-hepten-3-yl)phenyl ketone (6g): IR
(neat) 2955, 2862, 1659, 1605, 1412, 1281, 1180, 1026, 926, 841,
756, 702 cm-1; 1H NMR (CDCl3) δ -0.06 (s, 9H), 0.87 (t, J =
7.5 Hz, 3H), 1.12-1.37 (m, 4H), 1.69-1.76 (m, 1H), 1.82-1.89
(m, 1H), 3.51 (t, J = 7.5 Hz, 1H), 5.56 (dd, J = 2.0, 1.0 Hz, 1H),
5.78 (dd, J = 2.0, 1.5 Hz, 1H), 7.27-7.29 (m, 2H), 7.46-7.50 (m,
2H), 7.56-7.59 (m, 1H), 7.72-7.75 (m, 2H), 7.78-7.80 (m, 2H);
13C NMR (CDCl3) δ -0.9, 14.2, 23.0, 30.4, 34.9, 50.5, 124.4,
128.4, 128.6, 130.2, 130.4, 132.4, 135.6, 138.2, 150.0, 154.5,
196.8. Anal. Calcd for C23H30OSi: C, 78.80; H, 8.63. Found:
C, 78.72; H, 8.80.
4-(2-Trimethylsilyl-1-hepten-3-yl)benzonitrile (6h): IR (neat)
2955, 2862, 2230, 1605, 1504, 1412, 1250, 1026, 934, 841, 756
cm-1; 1H NMR (CDCl3) δ -0.09 (s, 9H), 0.85 (t, J = 7.5 Hz,
3H), 1.05-1.14 (m, 1H), 1.18-1.35 (m, 3H), 1.63-1.70 (m, 1H),
1.79-1.86 (m, 1H), 3.47 (t, J = 7.5 Hz, 1H), 5.57 (dd, J = 2.0,
1.0 Hz, 1H), 5.75 (dd, J = 2.0, 1.5 Hz, 1H), 7.26-7.29 (m, 2H),
7.55 (dt, J = 8.5, 2.0 Hz, 2H); 13C NMR (CDCl3) δ -0.9, 14.2,
22.9, 30.3, 34.8, 50.5, 110.1, 119.3, 124.9, 129.4, 132.2, 150.5,
154.0. Anal. Calcd for C17H25NSi: C, 75.21; H, 9.28. Found: C,
75.26; H, 9.31.
1
2-Phenyl-4-nonyn-2-ol (3): H NMR (CDCl3) δ 0.87 (t, J =
7.5 Hz, 3H), 1.28-1.36 (m, 2H), 1.39-1.45 (m, 2H), 1.61 (s, 3H),
2.14 (tt, J = 7.0, 2.5 Hz, 2H), 2.49 (s, 1H), 2.65 (dt, J = 17.0, 2.5
Hz, 1H), 2.72 (dt, J = 17.0, 2.5 Hz, 1H), 7.25 (tt, J = 7.0, 2.0 Hz,
1H), 7.32-7.36 (m, 2H), 7.46-7.49 (m, 2H); 13C NMR (CDCl3)
δ 13.8, 18.6, 22.1, 29.4, 31.2, 35.3, 73.5, 75.9, 84.5, 125.0, 127.1,
128.3, 147.0; HRMS (FAB) found 215.1433 (M - H), calcd for
C15H19O 215.1436.
Dimethylsilyl 1-methyl-1-phenyl-3-octynyl ether (4): 1H NMR
(CDCl3) δ 0.16 (d, J = 3.0 Hz, 3H), 0.21 (d, J = 3.0 Hz, 3H),
0.88 (t, J = 7.0 Hz, 3H), 1.31-1.45 (m, 4H), 1.75 (s, 3H), 2.12 (tt,
J = 7.0, 2.5 Hz, 2H), 2.62-2.64 (m, 2H), 4.74 (septet, J = 3.0
Hz, 1H), 7.24 (tt, J = 7.5, 1,5 Hz, 1H), 7.30-7.34 (m, 2H),
7.44-7.46 (m, 2H); 13C NMR (CDCl3) δ 0.7, 13.8, 18.7, 22.1,
27.8, 31.2, 36.3, 77.0, 77.2, 83.1, 125.6, 127.0, 128.0, 147.4;
HRMS (EI) found 274.1755, calcd for C17H26OSi 274.1753.
3-Phenyl-2-trimethylsilyl-1-heptene (6a): IR (neat) 3061,
3026, 2957, 2931, 2898, 2859, 1492, 1452, 1248, 926, 837, 760,
699 cm-1; 1H NMR (CDCl3) δ -0.09 (s, 9H), 0.86 (t, J = 7.5 Hz,
3H), 1.10-1.19 (m, 1H), 1.20-1.35 (m, 3H), 1.65-1.74 (m, 1H),
1.78-1.86 (m, 1H), 3.41 (t, J = 7.5 Hz, 1H), 5.51 (dd, J = 2.5,
1.0 Hz, 1H), 5.74 (dd, J = 2.5, 1.5 Hz, 1H), 7.14-7.19 (m, 3H),
7.24-7.28 (m, 2H); 13C NMR (CDCl3) δ -0.9, 14.3, 23.0, 30.4,
34.9, 50.5, 123.5, 126.1, 128.3, 128.7, 144.6, 155.2. Anal. Calcd
for C16H26Si: C, 77.97; H, 10.63. Found: C, 78.02; H, 10.85.
3-(4-Methylphenyl)-2-trimethylsilyl-1-heptene (6b): IR (neat)
2955, 2862, 1512, 1458, 1412, 1250, 926, 841, 756, 687 cm-1; 1H
NMR (CDCl3) δ -0.07 (s, 9H), 0.87 (t, J = 7.5 Hz, 3H),
1.11-1.38 (m, 4H), 1.64-1.72 (m, 1H), 1.77-1.84 (m, 1H),
2.32 (s, 3H), 3.39 (t, J = 7.5 Hz, 1H), 5.50 (dd, J = 2.5, 1.0 Hz,
1H), 5.73 (dd, J = 2.5, 1.5 Hz, 1H), 7.05-7.09 (m, 4H); 13C
NMR (CDCl3) δ -0.9, 14.3, 21.2, 23.0, 30.5, 35.1, 50.0, 123.4,
128.5, 129.0, 135.5, 141.5, 155.5. Anal. Calcd for C17H28Si: C,
78.38; H, 10.83. Found: C, 78.63; H, 10.68.
3-(4-Methoxyphenyl)-2-trimethylsilyl-1-heptene (6c): IR
(neat) 3676, 2956, 2858, 1610, 1510, 1302, 1248, 1179, 1041,
925, 836, 759 cm-1; 1H NMR (CDCl3) δ -0.09 (s, 9H), 0.86 (t,
J = 7.5 Hz, 3H), 1.10-1.35 (m, 4H), 1.61-1.68 (m, 1H), 1.75-
1.82 (m, 1H), 3.36 (t, J = 7.5 Hz, 1H), 3.79 (s, 3H), 5.48 (d, J =
2.0 Hz, 1H), 5.72 (s, 1H), 6.81 (d, J = 9.0 Hz, 2H), 7.07 (d, 9.0
Hz, 2H); 13C NMR (CDCl3) δ -0.9, 14.3, 23.0, 30.4, 35.1, 49.6,
55.4, 113.6, 123.2, 129.5, 136.6, 155.6, 158.1. Anal. Calcd for
C17H28OSi: C, 73.85; H, 10.21. Found: C,74.01; H, 10.33.
3-(4-Trifluoromethylphenyl)-2-trimethylsilyl-1-heptene (6d):
IR (neat) 2955, 2862, 1620, 1327, 1250, 1165, 1026, 1032, 841
cm-1; 1H NMR (CDCl3) δ -0.08 (s, 9H), 0.86 (t, J = 7.5 Hz,
3H), 1.08-1.16 (m, 1H), 1.18-1.35 (m, 3H), 1.65-1.72 (m, 1H),
1.80-1.87 (m, 1H), 3.48 (t, J = 7.5 Hz, 1H), 5.56 (dd, J = 2.0,
1.0 Hz, 1H), 5.75 (dd, J = 2.0, 1.5 Hz, 1H), 7.28 (d, J = 8.0 Hz,
2H), 7.51 (d, J = 8.0 Hz, 2H); 13C NMR (CDCl3) δ -0.9, 14.2,
22.9, 30.3, 34.9, 50.3, 124.5, 124.6 (q, J = 270.1 Hz), 125.2 (q,
J = 3.75 Hz), 128.6 (q, J = 32.18 Hz), 128.9, 148.9, 154.5. Anal.
Calcd for C17H25F3Si: C, 64.93; H, 8.01. Found: C, 64.67;
H, 8.06.
3-(1-Naphthyl)-2-trimethylsilyl-1-heptene (6i): IR (neat) 3055,
1
2955, 2862, 1597, 1396, 1250, 926, 841, 779 cm-1; H NMR
(CDCl3) δ -0.15 (s, 9H), 0.85 (t, J = 7.5 Hz, 3H), 1.20-1.40 (m,
4H), 1.80-1.87 (m, 1H), 1.93-1.99 (m, 1H), 4.30 (t, J = 7.0 Hz,
1H), 5.62 (dd, J = 2.5, 1.0 Hz, 1H), 5.78 (dd, J = 2.5, 1.5 Hz,
1H), 7.35 (dd, J = 7.5, 1.5 Hz, 1H), 7.40-7.51 (m, 3H), 7.70 (d,
J = 8.0 Hz, 1H), 7.84-7.86 (m, 1H), 8.12 (d, J = 8.5 Hz, 1H);
13C NMR (CDCl3) δ -0.7, 14.3, 23.2, 30.7, 34.9, 45.2, 123.8,
124.7, 125.4, 125.5 (overlapped, 2C), 125.8, 126.9, 129.1, 132.5,
134.3, 140.4, 154.6. Anal. Calcd for C20H28Si: C, 81.01; H, 9.52.
Found: C, 80.95; H, 9.46.
3-(3-Pyridyl)-2-trimethylsilyl-1-heptene (6j): IR (neat) 2955,
2862, 2368, 1574, 1466, 1420, 1250, 1111, 1026, 926, 841, 756,
718 cm-1; 1H NMR (CDCl3) δ -0.08 (s, 9H), 0.85 (t, J = 7.5 Hz,
3H), 1.09-1.18 (m, 1H), 1.19-1.37 (m, 3H), 1.64-1.72 (m, 1H),
1.82-1.88 (m, 1H), 3.43 (t, J = 7.5 Hz, 1H), 5.56 (dd, J = 2.5,
1.0 Hz, 1H), 5.75 (dd, J = 2.5, 1.0 Hz, 1H), 7.18-7.21 (m, 1H),
7.45-7.47 (m, 1H), 8.42-8.44 (m, 2H); 13C NMR (CDCl3) δ
-0.9, 14.2, 22.9, 30.3, 34.8, 47.8, 123.4, 124.6, 135.7, 139.9,
147.8, 150.5, 154.3. Anal. Calcd for C15H25NSi: C, 72.81; H,
10.18. Found: C, 72.70; H, 10.43.
2-Dimethylphenylsilyl-3-phenyl-1-heptene (6k): IR (neat)
3055, 2955, 2862, 1597, 1458, 1427, 1250, 1111, 1034, 934, 826,
772, 702 cm-1; 1H NMR (CDCl3) δ 0.11 (s, 3H), 0.19 (s, 3H),
0.79 (t, J = 7.5 Hz, 3H), 1.02-1.25 (m, 4H), 1.60-1.67 (m, 1H),
1.72-1.79 (m, 1H), 3.35 (t, J = 7.5 Hz, 1H), 5.55 (d, J = 2.5 Hz,
1H), 5.83 (dd, J = 1.5 Hz, 1H), 7.03-7.06 (m, 2H), 7.12-7.15
(m, 1H), 7.19-7.22 (m, 2H), 7.29-7.36 (m, 3H), 7.39-7.42 (m,
2H); 13C NMR (CDCl3) δ -2.5, -2.2, 14.2, 22.9, 30.3, 35.0,
50.3, 125.6, 126.1, 127.8, 128.2, 128.7, 129.0, 134.3, 138.6, 144.3,
153.5. Anal. Calcd for C21H28Si: C, 81.75; H, 9.15. Found: C,
81.56; H, 9.08.
Ethyl 4-(2-trimethylsilyl-1-hepten-3-yl)benzoate (6e): IR
(neat) 2955, 2870, 1720, 1612, 1273, 1180, 1111, 1026, 926,
841, 764 cm-1 1H NMR (CDCl3) δ -0.10 (s, 9H), 0.84 (t,
;
J = 7.5 Hz, 3H), 1.06-1.18 (m, 1H), 1.20-1.33 (m, 3H), 1.38 (t,
J = 7.0 Hz, 3H), 1.65-1.72 (m, 1H), 1.79-1.86 (m, 1H), 3.47
(t, J = 7.5 Hz, 1H), 4.36 (q, J = 7.0 Hz, 2H), 5.54 (dd, J = 2.0,
J. Org. Chem. Vol. 75, No. 13, 2010 4341

Wakabayashi et al.
JOCFeatured Article
The enantiomeric excess of 6k was determined after re-
placement of the silyl group with a phenyl group to give 6m by
the palladium-catalyzed cross-coupling reaction of 6k with
iodobenzene in the presence of potassium trimethylsiloxide
and 18-crown-6.15
134.4, 136.2, 152.0; HRMS (EI) found 270.1438, calcd for
C17H22OSi 270.1440; 92% ee R; [R]32 -65.0 (c 1.00, CHCl3).
D
HPLC conditions: Daicel CHIRALPAK AD-H, hexane/2-pro-
panol = 98.0/2.0, 0.4 mL/min, retention time: 28.01 min (S,
major); 30.30 min (R, minor).
2-Methyl-3-phenyl-1-heptene (6l): IR (neat) 3078, 3024, 2932,
2-(4-Methoxy-2-methylphenyl)-3-trimethylsilyl-3-butenyl trii-
sopropylsilyl ether (6q): IR (neat) 2947, 2862, 2361, 1612, 1504,
1466, 1381, 1250, 1111, 1057, 995, 926, 841, 756, 687 cm-1; 1H
NMR (CDCl3) δ 0.09 (s, 9H), 0.97-0.99 (m, 21H), 2.34 (s, 3H),
3.77 (s, 3H), 3.81-3.87 (m, 2H), 4.02 (dd, J = 5.0 Hz, 1H), 5.58
(dd, J = 2.5, 1.0 Hz, 1H), 5.74 (dd, J = 2.5, 1.0 Hz, 1H), 6.63-
6.69 (m, 2H), 7.04 (d, J = 8.5 Hz, 1H); 13C NMR (CDCl3)
δ -0.9, 12.2, 18.18, 18.19, 20.4, 47.5, 55.3, 66.5, 110.8, 115.9,
124.9, 129.5, 132.0, 138.0, 152.0, 158.0. Anal. Calcd for
C24H44O2Si2: C, 68.51; H, 10.54. Found: C, 68.71; H, 10.65.
Direct determination of the enantiomeric excess of 6q was
difficult. For the determination, we deprotected the silyl ether to
yield the corresponding alcohol 6q-Si (vide infra). Desilylation
was performed by treatment of 6q with tetrabutylammonium
fluoride in THF at room temperature (80% yield).
2862, 1643, 1597, 1450, 1373, 1034, 887, 748, 702 cm-1 1H
;
NMR (CDCl3) δ 0.87 (t, J = 7.5 Hz, 3H), 1.12-1.36 (m, 4H),
1.57 (m, 3H), 1.68-1.75 (m, 1H), 1.79-1.86 (m, 1H), 3.19 (t, J =
7.5 Hz, 1H), 4.81-4.82 (m, 1H), 4.90-4.91 (m, 1H), 7.17-7.22
(m, 3H), 7.26-7.30 (m, 2H); 13C NMR (CDCl3) δ 14.2, 21.1,
23.0, 30.3, 32.9, 53.1, 110.4, 126.3, 128.1, 128.4, 144.2, 148.5;
HRMS (EI) found 188.1568, calcd for C14H20 188.1565.
2,3-Diphenyl-1-heptene (6m): IR (neat) 3024, 2932, 2862,
1628, 1497, 1450, 1026, 903, 779, 702 cm-1; 1H NMR (CDCl3)
δ 0.85 (t, J = 7.5 Hz, 3H), 1.19-1.36 (m, 4H), 1.74-1.81 (m,
1H), 1.87-1.93 (m, 1H), 3.75 (t, J = 7.5 Hz, 1H), 5.18 (dd, J =
1.0 Hz, 1H), 5.36 (d, J = 1.0 Hz, 1H), 7.14-7.27 (m, 10H); 13
C
NMR (CDCl3) δ 14.2, 23.0, 30.4, 35.1, 50.7, 113.2, 126.3, 127.0,
127.3, 128.2, 128.4, 128.5, 143.0, 143.9, 152.2. Anal. Calcd for
C19H22: C, 91.14; H, 8.86. Found: C, 91.13; H, 9.03. HPLC
conditions: Daicel CHIRALPAK OJ-H, hexane/2-prop-
nol =98.0/2.0, 0.2 mL/min, retention time: 20.06 min (R,
major); 21.21 min (S, minor).
2-(4-Methoxy-2-methylphenyl)-3-trimethylsilyl-3-buten-1-ol
(6q-Si): IR (neat) 3410, 2955, 1612, 1497, 1466, 1412, 1250,
1
1196, 1057, 934, 841, 756, 694 cm-1; H NMR (CDCl3) δ 0.04
(s, 9H), 1.50 (t, J = 5.5 Hz, 1H), 2.33 (s, 3H), 3.74-3.81 (m, 4H),
3.91-3.96 (m, 2H), 5.66 (dd, J = 2.0, 1.0 Hz, 1H), 5.71 (dd, J =
2.0, 1.0 Hz, 1H), 6.71 (dt, J = 9.0, 3.0 Hz, 2H), 7.07 (d, J = 9.0
Hz, 1H); 13C NMR (CDCl3) δ -0.9, 20.2, 47.8, 55.3, 64.8, 111.2,
116.5, 125.6, 128.9, 130.5, 138.3, 152.0, 158.4; 92% ee R,
2-Phenyl-3-trimethylsilyl-3-butenyl triisopropylsilyl ether (6n):
IR (neat) 2947, 2869, 1466, 1381, 1250, 1111, 995, 926, 880, 841,
687 cm-1 1H NMR (CDCl3) δ -0.05 (s, 9H), 0.97-1.03
;
(m, 21H), 3.67 (t, J = 7.0 Hz, 1H), 3.93 (dd, J = 10.0, 7.0 Hz,
1H), 4.07 (dd, J = 10.0, 7.0 Hz, 1H), 5.59 (dd, J = 2.5, 1.0 Hz,
1H), 5.77 (dd, J = 2.5, 1.0 Hz, 1H), 7.17-7.20 (m, 1H),
7.22-7.28 (m, 4H); 13C NMR (CDCl3) δ -1.1, 12.2, 18.15,
18.19, 52.7, 67.0, 124.7, 126.4, 128.1, 129.2, 142.1, 152.2. Anal.
Calcd for C22H40OSi2: C, 70.14; H, 10.70. Found: C, 70.08; H,
10.77.
[R]32 -47.8 (c 0.75, CHCl3). Anal. Calcd for C15H24O2Si: C,
D
68.13; H, 9.15. Found: C, 68.40; H, 9.20. HPLC conditions:
Daicel CHIRALPAK OD-H, hexane/2-propanol = 99.4/0.6, 0.4
mL/min, retention time: 44.53 min (S, major); 51.98 min (R,
minor).
2-(9-Anthryl)-3-trimethylsilyl-3-butenyl triisopropylsilyl ether
(6r): IR (neat) 3055, 2947, 2862, 1466, 1389, 1250, 1103, 1011,
926, 880, 841, 733, 687 cm-1; 1H NMR (CDCl3) δ -0.43 (s, 9H),
0.74-0.89 (m, 21H), 4.43 (dd, J = 9.0, 6.5 Hz, 1H), 4.82 (dd, J =
9.0, 6.5 Hz, 1H), 5.18-5.21 (m, 1H), 5.73 (dd, J = 2.5 Hz, 1H),
6.04 (dd, J = 2.5 Hz, 1H), 7.40 (s, 4H), 7.95-7.97 (m, 2H), 8.35
(s, 1H), 8.47-8.49 (m, 2H); 13C NMR (CDCl3) δ -0.8, 12.0,
17.9, 18.0, 48.1, 66.6, 124.4, 124.7 (overlapped, 2C), 125.4, 127.3,
129.3, 131.6, 132.0, 134.2, 154.2. Anal. Calcd for C30H44OSi2: C,
75.56; H, 9.30. Found: C, 75.29; H, 9.17.
Direct determination of the enantiomeric excess of 6r was
difficult. For the determination, we deprotected the silyl ether to
yield the corresponding alcohol 6r-Si (vide infra). Desilylation
was performed by treatment of 6r with tetrabutylammonium
fluoride in THF at room temperature (84% yield).
4,4-Dimethyl-3-phenyl-2-trimethylsilyl-1-pentene (6o): IR
(neat) 2955, 1597, 1450, 1366, 1250, 1157, 1119, 1072, 1011,
1
841, 748, 694 cm-1; H NMR (CDCl3) δ 0.09 (s, 9H), 1.00 (s,
9H), 3.49 (d, J = 1.0 Hz, 1H), 5.63 (d, J = 4.0 Hz, 1H), 6.19 (dd,
J = 4.0, 1.0 Hz, 1H), 7.15-7.19 (m, 1H), 7.21-7.28 (m, 4H); 13
C
NMR (CDCl3) δ -1.2, 29.7, 35.6, 59.1, 124.9, 126.1, 127.4,
131.0, 141.9, 154.2. Anal. Calcd for C16H26Si: C, 77.97; H, 10.63.
Found: C, 77.77; H, 10.60.
2-(1-Naphthyl)-3-trimethylsilyl-3-butenyl triisopropylsilyl ether
(6p): IR (neat) 3055, 2947, 2862, 1466, 1389, 1250, 1111, 1010,
926, 841, 764, 687 cm-1 1H NMR (CDCl3) δ 0.14 (s, 9H),
;
0.93-1.00 (m, 21H), 4.05 (dd, J = 10.0, 6.5 Hz, 1H), 4.18 (dd,
J = 10.0, 6.5 Hz, 1H), 4.55 (t, J = 6.5 Hz, 1H), 5.68 (dd, J = 2.5,
1.0 Hz, 1H), 5.88 (J = 2.5, 1.0 Hz, 1H), 7.38-7.51 (m, 4H), 7.70
(dd, J = 6.5, 3.0 Hz, 1H), 7.82-7.84 (m, 1H), 8.17-8.19 (m, 1H);
13C NMR (CDCl3) δ -0.1, 12.2, 18.2, 47.7, 66.4, 124.0, 125.3,
125.3, 125.76, 125.79, 126.4, 127.1, 129.0, 132.7, 134.2, 137.6,
152.0. Anal. Calcd for C26H42OSi2: C, 73.17; H, 9.92. Found: C,
73.03; H, 10.05.
Direct determination of the enantiomeric excess of 6p was
difficult. For the determination, we deprotected the silyl ether to
yield the corresponding alcohol 6p-Si (vide infra). Desilylation
was performed by treatment of 6p with tetrabutylammonium
fluoride in THF at room temperature (84% yield).
2-(9-Anthryl)-3-trimethylsilyl-3-buten-1-ol (6r-Si): mp = 70-
71 °C; IR (Nujol) 3256, 2924, 2854, 2723, 1589, 1458, 1373,
1
1250, 1180, 1049, 972, 918, 841, 725 cm-1; H NMR (CDCl3)
δ -0.41 (s, 9H), 1.25 (dd, J = 8.0, 5.0 Hz, 1H), 4.45-4.50 (m,
1H), 4.72-4.77 (m, 1H), 5.25-5.28 (m, 1H), 5.78 (dd, J = 2.5,
2.0 Hz, 1H), 6.02 (dd, J = 2.5, 2.0 Hz, 1H), 7.45-7.48 (m, 4H),
8.01-8.03 (m, 2H), 8.44 (s, 1H), 8.50-8.52 (m, 2H); 13C NMR
(CDCl3) δ -1.0, 47.6, 65.6, 124.1, 125.0 (overlapped, 2C), 125.6,
128.1, 129.5, 131.6, 132.0, 132.1, 154.0; HRMS (EI) found
320.1594, calcd for C21H24OSi 320.1596; 91% ee R, [R]32
D
2-(1-Naphthyl)-3-trimethylsilyl-3-buten-1-ol (6p-Si): IR (neat)
3387, 3055, 2955, 2893, 1597, 1512, 1396, 1250, 1165, 1049, 934,
841, 779, 694 cm-1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 1.60 (t, J =
6.5 Hz, 1H), 4.01 (m, 1H), 4.11 (m, 1H), 4.63 (t, J = 7.0 Hz, 1H),
5.77 (dd, J = 2.5, 1.5 Hz, 1H), 5.87 (dd, J = 2.5, 1.5 Hz, 1H),
7.40-7.55 (m, 4H), 7.75-7.77 (m, 1H), 7.86-7.88 (m, 1H), 8.15
(dd, J = 8.0, 0.5 Hz, 1H); 13C NMR (CDCl3) δ -0.9, 47.8, 64.9,
123.6, 125.4, 125.7, 125.9, 126.33, 126.34, 127.8, 129.2, 132.4,
-124.3 (c 1.01, CHCl3). HPLC conditions: Daicel CHIRAL-
PAK OD-H, hexane/2-propanol =80/20, 1.0 mL/min, reten-
tion time: 5.92 min (S, major); 7.45 min (R, minor).
The absolute stereochemistry of the major isomer of 6r-Si was
determined by using X-ray crystallographic analysis. Crystals of
the major isomer of 6r-Si suitable for X-ray crystallographic
analysis were grown from heptane/dichloromethane. The OR-
TEP drawing of the major isomer of 6r-Si is shown in the
Supporting Information (CCDC No. 772243). The flack para-
meter was -0.20, which indicates that the structure shown
(15) Anderson, J. C.; Munday, R. H. J. Org. Chem. 2004, 69, 8971–8974.
4342 J. Org. Chem. Vol. 75, No. 13, 2010

Wakabayashi et al.
JOCFeatured Article
below represents the exact absolute stereochemistry, which is
S. The absolute stereochemistry of 6k-Si, 6p-Si, and 6q-Si was
tentatively asigned by taking the reaction mechanism into
consideration.
Program from JSPS. S.H. acknowledges JSPS for financial
support.
Supporting Information Available: Copies of NMR spectra
and HPLC chromatograms and CIF and ORTEP drawing for
6r-Si. This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgment. This work was supported by a Grant-
in-Aid for Scientific Research and Global COE Research
J. Org. Chem. Vol. 75, No. 13, 2010 4343