LETTER
Direct Allylation of Alcohols in Non-Halogenated Solvent
ture was poured into Et O (50 mL) and aq NaHCO
1739
References
2
3
(30 mL).
The solution was extracted with Et O and the organic layer
2
(
1) (a) Cella, J. A. J. Org. Chem. 1982, 47, 2125. (b) Schmitt,
A.; Reibig, H.-U. Eur. J. Org. Chem. 2000, 3893.
was dried over MgSO . The evaporation of the ether solution
4
gave the crude product, which was analyzed by NMR.
Product Data.
(c) Toshimitsu, A.; Nakano, K.; Mukai, T.; Tamao, K. J. Am.
Chem. Soc. 1996, 118, 2756. (d) Bisaro, F.; Prestat, G.;
Vitale, M.; Poli, G. Synlett 2002, 1823. (e) For the
asymmetric transformation of alcohol mediated by
titanium(IV) complex, see: Braun, M.; Kotter, W. Angew.
Chem. Int. Ed. 2004, 43, 514.
All products 3a–f are known compounds. The products
3
a–c showed spectra in an excellent agreement with our
3
previous reported data. The spectral data of 3d was in an
excellent agreement with the sample which is commercially
14
15
available. Our spectral data of 3e and 3f are shown below.
-Ferrocenyl-1-pentene (3e): according to the typical
(
(
2) Rubin, M.; Gevorgyan, V. Org. Lett. 2001, 3, 2705.
3) Yasuda, M.; Saito, T.; Ueba, M.; Baba, A. Angew. Chem. Int.
Ed. 2004, 43, 1414.
4) Non-halogenated solvents such as hexane, THF and DMF
provided less satisfactory results in the allylation of
benzhydrol (1b, see ref. 3).
5) (a) Onishi, Y.; Ito, T.; Yasuda, M.; Baba, A. Eur. J. Org.
Chem. 2002, 1578. (b) Onishi, Y.; Ito, T.; Yasuda, M.; Baba,
A. Tetrahedron 2002, 58, 8227.
4
procedure, this compound was prepared from 1e, 2, InCl3
and Me SiBr to give the product as a brown liquid after
3
(
(
(
(
chromatography(hexane). Further purification was
performed by distillation under reduced pressure; bp 95 °C/
–1
1
0
.1 mmHg. IR:(neat): 1639 (C=C) cm . H NMR (400
MHz, CDCl ): d = 5.78 (dddd, J = 17.9, 10.4, 7.7, 6.5 Hz, 1
3
A
H, 2-H), 5.00 (ddt, J = 17.9, 1.2, 1.2 Hz, 1 H, 1-H ), 4.99
ddt, J = 10.4, 1.2, 1.2 Hz, 1 H, 1-H ), 4.12–4.11 (m, 5 H,
B
(
6) (a) Miyai, T.; Onishi, Y.; Baba, A. Tetrahedron 1999, 55,
C H ), 4.06 (s, 4 H, C H ), 2.55 (ddq, J = 8.7, 5.1, 6.8 Hz, 1
5
5
5
4
1017. (b) Miyai, T.; Ohishi, Y.; Baba, A. Tetrahedron Lett.
A
H, 4-H), 2.36 (dddt, J = 13.8, 6.5, 5.1, 1.2 Hz, 1 H, 3-H ),
1998, 39, 6291.
B
2
.07 (dddt, J = 13.8, 8.7, 7.7, 1.2 Hz, 1 H, 3-H ), 1.21 (d,
7) (a) Mukaiyama, T.; Ohno, T.; Nishimura, T.; Han, J. S.;
13
J = 6.8 Hz, 3 H, 5-H3). C NMR (100 MHz, CDCl ): d =
3
Kobayashi, S. Bull. Chem. Soc. Jpn. 1991, 64, 2524.
137.38 (d, C-2), 115.71 (t, C-1), 95.33 (s, ipso-carbon in
(
b) Mukaiyama, T.; Ohno, T.; Han, J. S.; Kobayashi, S.
Chem. Lett. 1991, 20, 949.
8) In the allylation of 1-phenylethanol (1a) using B(C F ) ,
C H ), 68.35 (d, C H ), 66.96 (d), 66.92 (d), 66.80 (d), 65.93
5
4
5
5
(
d), 43.08 (t, C-3), 32.94 (d, C-4), 20.01 (q, C-5). MS (EI, 70
(
+
+
6
5
3
eV): m/z (%) = 254 (58)[M ], 213 (100) [M –
CH CH=CH ], 121 (23) [M – C H CH(CH )CH CH=CH ].
elimination of alcohol 1a to form styrene could readily occur
see ref. 3). Only a dimeric ether was obtained by InBr , see:
+
2
2
5
4
3
2
2
+
(
3
HRMS (EI, 70 eV): m/z calcd for C H Fe: 254.0758 [M ];
15 18
Kim, S. H.; Shin, C.; Pae, A. N.; Koh, H. Y.; Chang, M. H.;
Chung, B. Y.; Cho, Y. S. Synthesis 2004, 1581.
found: 254.0752. Anal. Calcd for C H Fe: C, 70.89; H,
1
5
18
7.14. Found: C, 70.60; H, 7.09.
(
9) For recent reviews on silicon Lewis acids, see: (a) Dilman,
A. D.; Ioffe, S. L. Chem. Rev. 2003, 103, 733. (b) Oishi, M.
In Lewis Acids in Organic Synthesis, Vol. 1; Yamamoto, H.,
Ed.; Wiley-VCH: Weinheim, 2000, 355–393.
3-Allylcyclohexene (3f): according to the typical procedure,
this compound was prepared from 1f, 2, InCl and Me SiBr
3
3
to give the product as a colorless liquid after distillation
under reduced pressure; bp 110 °C/100 mmHg. IR:(neat):
(
10) The allylation of alcohol in the presence of Yb(OTf) was
–1 1
3
1643 (C=C) cm . H NMR (400 MHz, CDCl ): d = 5.81
3
not promoted at all, although the enhancement of the Lewis
acidity using the combination of Yb(OTf) and Me SiCl was
(
ddt, J = 16.9, 10.1, 7.0 Hz, 1 H, 3-CH CH=CH ), 5.68 (ddd,
2 2
3
3
J = 10.1, 5.8, 3.6 Hz, 1 H, 1-H), 5.59 (dd, J = 10.1, 2.1 Hz, 1
H, 2-H), 5.05–4.99 (m, 2 H, 3-CH CH=CH ), 2.17–2.12 (m,
reported, see: Yamanaka, M.; Nishida, A.; Nakagawa, M.
Org. Lett. 2000, 2, 159.
2
2
1
H, 3-H), 2.06 (ddd, J = 13.0, 6.3, 6.3 Hz, 2 H, 3-
(
11) General Methods.
A
B
CH H CH=CH ), 2.05 (ddd, J = 13.0, 6.3, 6.3 Hz, 2 H, 3-
CH H CH=CH ), 2.00–1.94 (m, 2 H, 6-H ), 1.80–1.68 (m,
2
2
IR spectra were recorded as thin films on a HORIBA FT-720
A
B
2
2
1
13
spectrophotometer. H NMR and C NMR spectra were
obtained with TMS as internal standard. Mass spectra were
recorded on a JEOL JMS-DS303. MALDI-TOF MS was
measured on an Applied Biosystem Voyager RP using
dithranol matrix. Column chromatography was performed
on silica gel (Merck C60). Bulb-to-bulb distillation
A
A
B
H, 4-H and 5-H ), 1.58–1.47 (m, 1 H, 5-H ), 1.28–1.18
B
13
(
m, 1 H, 4-H ). C NMR (100 MHz, CDCl ): d = 137.25 (d,
3
3
3
2
-CH CH=CH ), 131.39 (d, C-2), 127.2 (d, C-1), 115.71 (t,
2 2
-CH CH=CH ), 40.65 (t, 3-CH CH=CH ), 35.01 (d, C-3),
2
2
2
2
8.80 (t, C-4), 25.27 (t, C-6), 21.41 (t, C-5). MS (EI, 70 eV):
+
+
m/z (%) = 122 (6) [M ], 81 (100) [M – CH CH=CH ], 79
2
2
(Kugelrohr) was accomplished in a Sibata GTO-250RS at
(
[
22). HRMS (EI, 70 eV): m/z calcd for C H : 122.1096
M ]; found: 122.1091.
9 14
the oven temperature and pressure indicated. Yields were
+
1
determined by H NMR using internal standards.
(
12) Elimination of alcohols 1e occurred in the presence of
combined Lewis acid in hexane to give polyvinylferrocene
rather than the desired product. Polyvinylferrocene was
identified by MALDI-TOF MS analysis.
Typical Procedure for Allylation of 1a (Table 2, Entry 1).
To a mixture of InCl (0.05 mmol) and 1-phenylethanol (1a,
3
1.0 mmol) in hexane (1 mL) was added allyltrimethylsilane
(
2, 2.0 mmol) and Me SiBr (0.1 mmol) under nitrogen. The
3
(13) Large-Scale Synthesis of 3a.
reaction mixture was stirred under the reaction conditions
To a mixture of InCl (5 mmol), Me SiBr (10 mmol) and
3
3
noted in the text. The resulting mixture was poured into Et O
2
allyltrimethylsilane 2 (300 mmol) in hexane (100 mL) was
slowly added a solution of 1a (100 mmol) in hexane (100
mL) for 1 h under nitrogen at 50 °C. After further stirring for
(
50 mL) and aq NaHCO (30 mL). The solution was
3
extracted with Et O and the organic layer was dried over
2
MgSO . The evaporation of the ether solution gave the crude
4
1 h at 50 °C, aq NaHCO (100 mL) was added to the reaction
3
product, which was analyzed by NMR.
Typical Procedure for Allylation by Slow Addition of 1a
mixture. The mixture was extracted with Et O and the
2
organic layer was dried over MgSO . The evaporation of the
4
(Table 2, Entry 2).
ether solution followed by the distillation (34 °C/1.5 mmHg)
gave the allylated product 3a in 84% yield (12.3g).
To a mixture of InCl (0.05 mmol), Me SiBr (0.1 mmol) and
3
3
allyltrimethylsilane (2, 3.0 mmol) in hexane (1 mL) was
slowly added a solution of 1-phenylethanol (1a, 1.0 mmol)
in hexane (1 mL) for 10 min at 50 °C under nitrogen. The
reaction mixture was stirred for 110 min. The resulting mix-
(
(
14) Jong, S.-J.; Fang, J.-M. J. Org. Chem. 2001, 66, 3533.
15) Tseng, C. C.; Paisley, S. D.; Goering, H. L. J. Org. Chem.
1986, 51, 2884.
Synlett 2005, No. 11, 1737–1739 © Thieme Stuttgart · New York