Rhenium complex-catalyzed carbon-carbon formation of alcohols and organosilicon compounds

Article abstract of DOI:10.1016/j.tetlet.2018.02.019

The coupling reactions of allylic and benzylic alcohols and allyltrimethylsilane are efficiently catalyzed by a rhenium complex to give the corresponding 1,5-dienes and alkenes in moderate to good yields. Similarly, alcohols were coupled with ketene silyl acetals to form the corresponding esters.

Full text of DOI:10.1016/j.tetlet.2018.02.019

Accepted Manuscript
Rhenium complex-catalyzed carbon-carbon formation of alcohols and organo-
silicon compounds
Rui Umeda, Toshifumi Jikyo, Kazuki Toda, Issey Osaka, Yutaka Nishiyama
PII:
S0040-4039(18)30186-2
https://doi.org/10.1016/j.tetlet.2018.02.019
TETL 49704
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
22 December 2017
4 February 2018
8 February 2018
Please cite this article as: Umeda, R., Jikyo, T., Toda, K., Osaka, I., Nishiyama, Y., Rhenium complex-catalyzed
carbon-carbon formation of alcohols and organosilicon compounds, Tetrahedron Letters (2018), doi: https://doi.org/
10.1016/j.tetlet.2018.02.019
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
Rhenium complex-catalyzed carbon-carbon
formation of alcohols and organosilicon
compounds
Leave this area blank for abstract info.
Rui Umeda, Toshifumi Jikyo, Kazuki Toda, Issey Osaka and Yutaka Nishiyama*
cat. ReBr(CO)5
OH
SiMe3
+
Ar
R
Ar
R
O
R2
R2
OSiR3
cat. ReBr(CO)5
3
OH
R1
OMe
R2
+
OMe
R1
Ph
Ph
R2

1
Tetrahedron Letters
Rhenium complex-catalyzed carbon-carbon formation of alcohols and organosilicon
compounds
Rui Umeda,a Toshifumi Jikyo,a Kazuki Toda,a Issey Osakab and Yutaka Nishiyamaa
a Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan
b Center for Nano Materials and Technology, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa 923-1292, Japan
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The coupling reactions of allylic and benzylic alcohols and allytrimethylsilane are efficiently
catalyzed by a rhenium complex to give the corresponding 1,5-dienes and alkenes in moderate to
good yields. Similarly, alcohols were coupled with ketene silyl acetals to form the corresponding
esters.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Rhenium
Alcohols
Allylsilane
Alkenes
The Lewis acid mediated and catalyzed coupling reaction of
various substrates with organosilicon compounds is a reliable and
widely used method for constructing carbon-carbon bonds in
organic synthesis. The use of inexpensive and readily available
compounds, such as alcohols, is highly desirable for the
reactions, especially from the view point of the sustainable
chemistry. However, catalytic substitution of the hydroxy group
in alcohols is difficult due to their poor leaving ability, which
requires equivalent or excess amounts of a Lewis acid. Recently,
the Lewis acid-catalyzed substituted reaction of alcohols with
organosilicon compounds has been developed; however, there are
some drawbacks of these methods; (i) limitation of the substrates,
(ii) instability under a moist or air condition, and (iii) the use of
excess amounts of the allylsilane (1.5 or 2.0 equiv.). 1-5
a rhenium catalyst, we discovered the rhenium complex-
catalyzed allylation of allylic and benzylic alcohols and their
derivatives with an allylsilane (Scheme 1).7-10 In addition,
alcohols were also coupled with ketene silyl acetals to give the
corresponding esters.11
We first investigated the effects of the rhenium complex,
reaction temperature and solvent on the coupling reaction of 1,3-
diphenylprop-2-en-1-ol (1a) and allyltrimethylsilane (2a) (Table
1). When 1a and one equivalent amount of 2a were stirred with a
catalytic amount of ReBr(CO)5 (5 mol%) in a 1,2-dichloroethane
solvent under an atmosphere of nitrogen at 80 °C for 2 h, the
coupling reaction of 1a and 2a proceeded to give 1,3-diphenyl-
1,5-hexadiene (3a) in 90% yield (Entry 1). The yield of 3a was
improved by using a small excess amount of 2a, and 3a (1.2
equiv.) was obtained in 96% yield (Entry 2). Even when the
reaction was carried out under an air atmosphere, the coupling
reaction proceeded to give 3a in 94% yield (Entry 3). For the
lower reaction temperatures (60 and 40 °C), the yield of 3a
significantly decreased (Entries 4 and 5). When toluene, hexane,
and 1,4-dioxane were used as the solvent, the reaction occurred
to give 2a in 25~80% yields (Entries 6-8). In the case of THF,
acetonitrile and DMF, the reaction did not proceed at all (Entries
9-11). The use of CH2ClCH2Cl as the solvent led to the highest
yield of 2a (Entry 2). When ReCl(CO)5 was used instead of
ReBr(CO)5 as the catalyst, 3a was obtained in 94% yield (Entry
12). In the case of other rhenium complexes, such as ReCl5 and
Re2O7, 3a was formed in 73 and 67% yields; however, Re2(CO)10
hardly exhibited any catalytic activity for the reaction (Entries
13-15).
cat. ReBr(CO)5
OH
SiMe3
+
Ar
R
Ar
R
O
R2
OSiR3
cat. ReBr(CO)5
3
R2
OMe
OH
R1
R2
+
OMe
Ph
Ph
R1
R2
Scheme 1
We recently reported that ReX(CO)5 (X = Cl or Br) serves as a
catalyst for the -alkylation of enol acetates with alcohols giving
the corresponding -alkylated carbonyl compounds.6 Based on
the continuous studies of the direct conversion of alcohols using
———
 Corresponding author. Tel.: +81 6 6368 0902; fax: +81 6 6339 4026; e-mail: nishiya@kansai-u.ac.jp

2
Tetrahedron
Table 2. Reaction of allylic alcohols 1 with
Table 1. Reaction of 1,3-diphenylprop-2-en-1-ol (1a) and
allyltrimethylsilane (2a)a
allyltrimethylsilane (2a)a
cat. ReBr(CO)5
OH
cat.Re complex
OH
SiMe3
+
SiMe3
+
Ph
Ph
R
R
R
R
Solvent
Ph
Ph
1a
2a
3a
2a
1
3
Entry
1c
Catalyst
Solvent
Temp (ºC)
80
Yield (%)b
Entry
1
Allylic alcohols
Products (%)b
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReBr(CO)5
ReCl(CO)5
ReCl5
CH2ClCH2Cl
CH2ClCH2Cl
CH2ClCH2Cl
CH2ClCH2Cl
CH2ClCH2Cl
toluene
90
96 (92)
94
16
16
80
25
35
0
OH
2
80
Ar
Ar
3d
80
Ar
Ar
Ar = Ph(1a)
92 (3a)
78 (3b)
83 (3c)
87 (3d)
16 (3e)
84 (3f)
4
60
2
3
4
5
6
Ar = 4-CH3C6H4 (1b)
X = 3-CH3C6H4 (1c)
X = 2-CH3C6H4 (1d)
X = 4-CH3OC6H4 (1e)
X = 4-ClC6H4 (1f)
OH
5
40
6
80
7
C6H14
80
8
1,4-dioxane
THF
80
9
80
10
11
12
13
14e
15e
CH3CN
80
0
Ar1
Ar2
Ar2
41 (3g’)
Ar1
DMF
80
0
Ar1
24 (3g)
Ar2
Ar1 = Ph
CH2ClCH2Cl
CH2ClCH2Cl
CH2ClCH2Cl
CH2ClCH2Cl
80
94
73
67
15
7
8
Ar2 = 4-CH3C6H4 (1g)
Ar1 = 4-CH3C6H4
Ar2 = Ph (1h)
80
Re2O7
80
Re2(CO)10
80
Ar2
29 (3g)
Ar1
Ar1
Ar1
Ar1
Ar1
Ar1
50 (3g’)
Ar2
Ar2
Ar2
Ar2
Ar2
a Reaction conditions: 1a (0.20 mmol), 2a (0.24 mmol), Re
catalyst (5 mol%), solvent (5 mL), 2 h under an atmosphere of
N2. b GLC yield. The number in parenthesis shows the isolated
9c
Ar1 = Ph
Ar2 = 4-CH3OC6H4 (1i)
c
d
Ar2
45 (3i’)
Ar1
24 (3i)
yield. 2a (0.20 mmol) was used. The reaction was carried out
under an air atmosphere. e Re catalyst (2.5 mol%) was used.
10c
11c
12
Ar1 = 4-CH3OC6H4
Ar2 = Ph (1j)
Ar2
29 (3i)
The rhenium complex is a useful catalyst for the synthesis of
1,5-dienes by the coupling reaction of allylic alcohols and
allyltrimethylsilane (2a). These results are shown in Table 2.12
For the reaction of the 1,3-diaryl substituted allyl alcohols
bearing electron-donating groups on both aromatic rings, such as
1,3-bis(4-methylphenyl)-, 1,3-bis(3-methylphenyl)-, and 1,3-
bis(2-methylphenyl)-prop-2-en-1-ol, 1,3-diaryl substituted 1,5-
hexadienes, 3b, 3c, 3d, were formed in 78, 83, and 87% yields,
respectively (Entries 2-4). However, for the reaction of 1,3-bis(4-
methoxyphenyl)-prop-2-en-1-ol bearing stronger electron
donating group than the methyl group on the aromatic ring, the
yield of 1,5-diene, 3e, was low due to the formation of
complicated by-products (Entry 5). In the case of 1,3-bis(4-
chlorophenyl)prop-2-en-1-ol, in which the electron withdrawing
group was substituted on both aromatic rings, 1,3-di(4-
chlorophenyl)-1,5-diene, 3f, was obtained in 84% yield (Entry 6).
For the reaction of 3-(4-methylphenyl)-1-phenylprop-2-en-1-ol
bearing two different aryl groups on the allyl alcohol, the mixture
of 1-(4-methylphenyl)-3-phenyl-1,5-hexadiene (3g) and 3-(4-
methylphenyl)-1-phenyl-1,5-hexadiene (3g’) (3g:3g’ = 24:41)
was formed in 65% yield (Entry 7). When 1-(4-methylphenyl)-3-
phenylprop-2-en-1-ol was allowed to react with 2a, the ratio of
3g and 3g’ was almost the same as that of the reaction of 3-(4-
methylphenyl)-1-phenylprop-2-en-1-ol (Entry 8). This tendency
was observed for the reaction of various allylic alcohols (Entries
9-14). For the reaction of 3-phenylprop-2-en-1-ol, the 1,5-diene,
3e, was not obtained due to the formation of complicated by-
products (Entry 15).
Ar1
48 (3i’)
Ar1 = 4-ClC6H4
Ar2 = Ph (1k)
Ar2
45 (3k’)
Ar1
26 (3k)
Ar1 = Ph
Ar2 = 4-ClC6H4 (1l)
Ar2
29 (3k)
Ar1
48 (3k’)
13c,d
14c,d
15
Ar = Ph
R = CH3 (1m)
R
Ar
Ar
R
1
9 (3m)
47 (3m’)
R = CH3
Ar = Ph (1n)
Ar
R
R
Ar
45 (3m’)
15 (3m)
R = H
Ar = Ph (1o)
Ar
R
R
Ar
0 (3o)
0 (3o’)
aReaction conditions: 1 (0.20 mmol), 2a (0.24 mmol),
ReBr(CO)5 (5 mol%), CH2ClCH2Cl (5 mL) at 80 ºC for 2 h under
an atmosphere of N2. bIsolated yield. 2a (0.4 mmol) was used.
c
dCH2ClCH2Cl (2mL) was used.

3
Ph
Ph
Ph
Ph
cat. ReBr(CO)5
(5 mol%)
O
The allylation of the other alcohols with allyltrimethylsilane
(2a) was examined, and these results are shown in Scheme 2.
Primary, secondary, and tertiary benzylic alcohols were
efficiently coupled with 2a to give the corresponding alkenes in
75, 86, and 95% yields, respectively. Unfortunately, a simple
aliphatic alcohol, such as 2-octanol, was not applicable for the
rhenium-catalyzed reaction system.
SiMe3
+
+
CH2ClCH2Cl (5 mL)
80 oC, 24 h
Ph
Ph
4a (0.10 mmol)
(0.24 mmol)
(3r) 88% (0.18 mmol)
O
cat. ReBr(CO)5
(5 mol%)
O
Ph
SiMe3
CH2ClCH2Cl (5 mL)
80 oC, 24 h
Ph
Ph
Ph
Ph
cat. ReBr(CO)5
(5 mol%)
4b (0.20 mmol)
(0.24 mmol)
(3r) 84%
SiMe3
+
4-CH3OC6H4
Scheme 4
4-CH3OC6H4
(0.20 mmol)
OH
CH2ClCH2Cl (5 mL)
80 oC, 7 h
(3p) 52%
2a (0.24 mmol)
The rhenium complex also acts as a catalyst for the coupling
reaction of diphenylmethanol and 1,3-diphenylprop-2-en-1-ol
and ketene silyl acetal to produce the corresponding esters, 5a, b,
in 84 and 70% yields, respectively (Scheme 5). The -
trisubstituted ester 5c was efficiently produced by this rhenium
catalytic method.
cat. ReBr(CO)5
(5 mol%)
OH
+
2a
CH2ClCH2Cl (5 mL)
80 oC, 9 h
Ph
Ph
(3q) 75%
(0.20 mmol)
(0.24 mmol)
cat. ReBr(CO)5
(5 mol%)
OH
+
+
2a
O
CH2ClCH2Cl (5 mL)
80 oC, 24 h
Ph
Ph
Ph
Ph
cat. ReBr(CO)5
OSitBuMe2
(0.24 mmol)
(0.20 mmol)
(10 mol%)
OH
Ph
(3r) 86%
OMe
Ph
+
cat. ReBr(CO)5
(5 mol%)
OMe
toluene (2 mL)
100 oC, 4 h
Ph
Ph
OH
2a
(0.20 mmol)
(0.40 mmol)
(5a) 84%
CH2ClCH2Cl (5 mL)
80 oC, 25 h
Ph
Ph
Ph
Ph
Ph
Ph
(0.24 mmol)
O
cat. ReBr(CO)5
(10 mol%)
OSitBuMe2
OMe
(0.20 mmol)
(3s) 95%
OH
OMe
Ph
cat. ReBr(CO)5
(5 mol%)
+
OH
toluene (2 mL)
100 oC, 4 h
Ph
Ph
Ph
+
2a
nC9H19 CH3
(0.20 mmol)
nC9H19
CH3
CH2ClCH2Cl (5 mL)
80 oC, 24 h
(0.20 mmol)
(0.40 mmol)
(5b) 70%
(0.24 mmol)
(3t) 0%
O
cat. ReBr(CO)5
(10 mol%)
Scheme 2
OSiMe3
OMe
OH
OMe
+
The allylation of alcohol with various allylic silane was
examined, and these results are shown in Scheme 3. When 1,3-
diphenylprop-2-en-1-ol
trimethylsilyl-1-propene the coupling reaction proceeded
smoothly to give the corresponding coupling product, (E)-5-
methyl-1,3-diphenyl-1,5-hexadiene (3u), in 95% yield. For the
toluene (2 mL)
100 oC, 4 h
Ph
Ph
Ph
Ph
(0.20 mmol)
(0.40 mmol)
(5c) 61%
was
treated
with
2-methyl-3-
Scheme 5
To obtain information about the reaction pathway regarding
the coupling of alcohol and trimethylallylsilane, the time-
dependence of the product was followed by GC analysis at the
appropriate time intervals. In the case of 1-phenylethanol, at the
early stage of the reaction, the GC analysis showed the formation
of bis(1-phenylethyl)ether. In contrast, for the reaction of 1,3-
dipehylprop-2-ene-1-ol, the formation of the dehydration
dimerized product was not observed. Based on these results, we
proposed the following two reaction pathways.13 The
decarbonylation of ReBr(CO)5 to form ReBr(CO)4, which is the
coordinative unsaturated 16-electron complex, is the first step of
the catalytic reaction.14 For the reaction of 1-phenylethanol, the
coordination of rhenium species to the oxygen atom of ether,
which is in situ formed by the intermolecular dehydration of
alcohol, followed by the C-O bond cleavage of ether generates
the stable carbocation.15 On the other hand, in the case of 1,3-
dipehylprop-2-ene-1-ol, the coordination of rhenium species to
the oxygen atom of alcohols followed by the C-O bond cleavage
of alcohols generates the stable carbocation.16 The carbocation
was coupled with allyltrimethylsilane or ketene silyl acetal to
give the corresponding alkenes or esters.
reaction
of
1-phenyl-3-trimethylsilyl-1-propene,
the
diphenylmethanol was selective coupled with the allylic silane to
give the 3,4,4-triphenyl-1-butene (3v) without the formation of
1,4,4-triphenyl-1-butene.
cat. ReBr(CO)5
(5 mol%)
OH
SiMe3
+
Ph
Ph
CH2ClCH2Cl (5 mL)
80 oC, 2 h
Ph
Ph
Ph
(3u) 95%
1a (0.20 mmol)
2a (0.24 mmol)
cat. ReBr(CO)5
(5 mol%)
Ph
OH
+
Ph
SiMe3
Ph
Ph
CH2ClCH2Cl (5 mL)
80 oC, 2 h
Ph
(3v) 78%
2b (0.24 mmol)
(0.20 mmol)
Scheme 3
The reactions of alcohol derivatives, such as ether and ester,
and allyltrimethylsilane (2a) were next examined and these
results are shown in Scheme 4. When bis(diphenylmethyl) ether
(4a) (0.10 mmol) was treated with a 2.4 equivalent amount of 2a,
4,4-diphenyl-1-butene (3r) was obtained in 0.18 mmol. This
result shows that both alkyl groups on the ether are efficiently
used during the reaction. The ester 4b was also allylated by 2a to
give 3r in 84% yield along with the formation of benzoic acid
(79%).
We report the rhenium complex-catalyzed coupling reaction of
alcohols with allyltrimethylsilane or ketene silyl acetals to give
the corresponding alkenes or esters. The application of the
reaction and determining the reaction pathway are now in
progress.

4
Tetrahedron
16) We have investigated the reaction of the allylic alcohol, such as 1,3-
References and notes
dipehyl-prop-2-en-1-ol, with anisole in the presence of ReBr(CO)5
catalyst, due to clear the formation of cation., the allylated product of
anisole was formed in 45 % yield.
1) In 1982, Cella J. A. reported the BF3-assisted allylation of alcohols with
allyl silane. See: Cella, J. A. J. Org. Chem. 1982, 47, 2125-2130.
2) (a) Rubin, M.; Gevorgyan, V. Org. Lett. 2001, 3, 2705-2707. (b)
Luzung, M. R.; Toste, F. D. J. Am. Chem. Soc. 2003, 125, 15760-15761.
(c)Braun, M.; Kotter, W. Angew. Chem. Int. Ed. 2004, 43, 514-517. (d)
Yasuda, M.; Saito, T.; Ueba, M.; Baba, A. Angew. Chem. Int. Ed. 2004,
43, 1414-1416. (e) Kim, S. H.; Shin, C.; Pai, A. N.; Koh, H. K.; Chang,
M. H.; Chung, B. Y.; Cho, Y. S. Synthesis, 2004, 1581-1584. (f) De, S.
K.; Gibbs, R. A. Tetrahedron Lett. 2005, 46, 8345-8350. (g) Sharma, G.
V. M.; Reddy, K. L.; Lakshmi, P. S.; Ravi, R.; Kunmar, A. C. J. Org.
Chem. 2006, 71, 3967-3969. (h) Saito, T.; Nishimoto, Y.; Yasuda, M.;
Baba, A. J. Org. Chem. 2006, 71, 8516-8522. (i) Kuninobu, Y.; Ishii,
E.; Takai, K. Angew. Chem. Int. Ed. 2007, 46, 3296. (j) Han, J.; Cui, Z.;
Wang, J.; Li, Z. Synth. Commun. 2010, 40, 2042-2046.
3) Rhenium-catalyzed allylation of propagyl alcohols with the allyl silane
has been reported. However, there is only one example of the allylation
of aliphatic alcohol and no example of allylation of the allylic alcohol.
See: Ref 2i.
4) The Brønsted acid catalyzed allylation of alcohols with the allyl silane
has also been reported. (a) Kaur, G.; Kaushik, M.; Trehan, S.
Tetrahedron Lett. 1997, 38, 2521-2524. (b) Motokura, K.; Nakagiri, N.;
Mizugaki, T.; Ebitani, K.; Kaneda, K. J. Org. Chem. 2007, 72, 6006-
6015. (c) Kadam, S. T.; Lee, H.; Kim, S. S. Appl. Organomet. Chem.
2010, 24, 67-70.
5) Baeza and Najera et al. have recently shown that the fluorinated alcohol
prompted substitution reaction of allylic alcohols with silylated
nucleophiles under metal-free conditions. See: Trillo, P.; Baeza, A.;
Najera, C. J. Org. Chem. 2012, 77, 7344-7354.
6) Umeda, R.; Takahashi, Y.; Nishiyama, Y. Tetrahedron Lett. 2014, 55,
6113-6116.
7) The Lewis acid-catalyzed allylated method of allyl silyl ether,10 alkyl
allyl ether,11 alkyl benzyl ether,11b,c and alkyl propagyl ethers12 with allyl
silane has been developed.
8) Yokozawa, T.; Furuhashi, K.; Natsume, H. Tetrahedron Lett. 1995, 36,
5243-5246.
9) (a) Murakami, M.; Kato, T.; Mukaiyama, T. Chem. Lett. 1987, 1167-
1170. (b) Fan, X.; Cui, X.-M.; Guan, Y.-H.; Fu, L.-A.; Lv, H.; Guo, K.;
Zhu, H.-B. Eur. J. Org. Chem. 2014, 498-501. (c) Sawama, Y.; Goto,
R.; Nagata, S.; Shishido, Y.; Monguchi, Y.; Sajiki, H. Chem. Eur. J.
2014, 20, 2631-2636.
10) Hayashi, M.; Inubushi, A. Chem. Lett. 1987, 1975-1978.
11) The Lewis acid-catalyzed coupling reaction of alcohols and ketene silyl
acetal. See: (a) Devineau, A.; Pousse, G.; Taillier, C.; Blanchet, J.;
Rouden, J.; Dalla, V. Adv. Synth. Catal. 2010, 352, 2881-2886; (b)
David S. Weinstein,D.S.; Gong, H.; Doweyko, A. M.; Cunningham, M.;
Habte, S.; Wang, J. H.; Holloway, D. A.; Burke, C.; Gao, L.; Guarino,
V.; Carman, J.; Somerville, J. E.; Shuster, D.; Salter-Cid, L.; Dodd, J.
H.; Nadler, S. G.; Barrish, J. C. J. Med. Chem. 2011, 54, 7318-7333; (c)
Hai-Yun Xiao, H.-Y.; Wu, D.-R.; Sheppeck II, J. E.; Habte, S. F.;
Cunningham, M. D.; Somerville, J. E.; Barrish, J. C.; Nadler, S. G.;
Dhar, T. G. M. Bioorg. Med. Chem. Lett. 2013, 23, 5571-5574; (d)
Conlon, D. A.; Natalie, K. J., Jr.; Cuniere, N.; Razler, T. M.; Zhu, J.; de
Mas, N.; Tymonko, S.; Fraunhoffer, K. J.; Sortore, E.; Rosso, V. W.;
Xu, Z.; Adams, M. L.; Patel, A.; Huang, J.; Gong, H.; Weinstein, D. S.;
Quiroz, F.; Chen, D. C. Org. Process Res. Dev. 2016, 20, 921-933.
12) General procedure: a 1,2-dichloroethane (2 mL) solution of alcohol (0.2
mmol), allyltrimethylsilane (0.24 mmol), and ReBr(CO)5 (5 mol%) was
stirred under an atmosphere of nitrogen at 80 oC for 1 h. After the
reaction was completed, H2O was added to the reaction mixture and
extracted with ethyl acetate. The organic layer was dried with MgSO4.
The resulting mixture was filtered, and the filtrate was concentrated.
Purification of the residue by silica gel column chromatography
afforded alkenes. Further purification was carried out by recyclable
preparative HPLC, if necessary.
13) For the rhenium-catalyzed reaction of alcohols and enol acetate, we
proposed the reaction pathway including the formation of ethers. See:
Ref. 6.
14) (a) Abel, E. W.; Hargreaves, G. B.; Wilkinson, G. J. Chem. Soc. 1958,
3149; (b) Jolly, P. W.; Stone, F. G. A. J. Chem. Soc. 1965, 5259; (c)
Zingales, F.; Sartorelli, U.; Canziani, F.; Raveglia, M. Inorg. Chem.
1967, 6, 154.
15) We have shown that the C-O bond of ethers was effectively cleaved by
the rhenium complex. See (a) Umeda, R.; Nishimura, T.; Kaiba, K.;
Tanaka, T.; Takahashi, Y.; Nishiyama, Y. Tetrahedron 2011, 67, 7217-
7221. (b) Umeda, R.; Kaiba, K.; Tanaka, T.; Takahashi, Y.; Nishimura,
T.; Nishiyama, Y. Synlett, 2010, 3089-3091.

5
Highlights
A new catalytic ability of rhenium complex is
described.
A new method for the formation of 1,5-diene and
alkenes is developed.
A rhenium-catalyzed carbon-carbon bond
formation of alcohols and organosilicons smoothly
proceeded.