Rhenium-catalyzed α-alkylation of enol acetates with alcohols or ethers

Article abstract of DOI:10.1016/j.jorganchem.2018.09.010

When benzylic and allylic alcohols were treated with enol acetate in the presence of a catalytic amount of a rhenium complex, ReBr(CO)₅, the carbon-carbon bond formation of the alcohols and enol acetate smoothly proceeded to give the corresponding ketones and aldehyde in moderate to good yields. For the reaction of allylic alcohols, γ,δ-unsaturated carbonyl compounds were obtained in good yields. When ethers were used instead of alcohols as the alkylated agent, two alkyl moieties on the ethers were utilized on the reaction.

Full text of DOI:10.1016/j.jorganchem.2018.09.010

Accepted Manuscript
Rhenium-catalyzed α-alkylation of enol acetates with alcohols or ethers
Rui Umeda, Yuuki Takahashi, Takaaki Yamamoto, Hideki Iseki, Issey Osaka, Yutaka
Nishiyama
PII:
S0022-328X(18)30671-5
10.1016/j.jorganchem.2018.09.010
JOM 20567
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 30 July 2018
Revised Date: 10 September 2018
Accepted Date: 17 September 2018
Please cite this article as: R. Umeda, Y. Takahashi, T. Yamamoto, H. Iseki, I. Osaka, Y. Nishiyama,
Rhenium-catalyzed α-alkylation of enol acetates with alcohols or ethers, Journal of Organometallic
Chemistry (2018), doi: https://doi.org/10.1016/j.jorganchem.2018.09.010.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Rhenium-Catalyzed α-Alkylation of Enol Acetates with Alcohols or Ethers
Rui Umeda,a Yuuki Takahashi,a Takaaki Yamamoto,a Hideki Iseki,a Issey Osaka,b and Yutaka Nishiyama*a
a Faculty of Chemistry, Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan
b Department of Pharmaceutical Engineering, Faculty of Engineering, Toyama Prefectural University, Imizu,
Toyama 939-0398, Japan
Key Words: rhenium, enol acetate, alcohol, ether, carbonyl compound
Abstract: When alcohols were treated with enol acetate in the presence of a catalytic amount of a rhenium
complex, ReBr(CO)5, the carbon-carbon bond formation of the alcohols and enol acetate smoothly
proceeded to give the corresponding ketones and aldehyde in moderate to good yields. For the reaction of
allylic alcohols, γ,δ-unsaturated carbonyl compounds were obtained in good yields. When ethers were used
instead of alcohols as the alkylated agent, two alkyl moieties on the ethers were utilized on the reaction.
1. Introduction
The α-alkylation of carbonyl compounds is one of the useful synthetic methods of α-alkyl substituted
carbonyl compounds, and various α-alkylation methods of carbonyl compounds have been reported [1].
Although the reaction of enolates and enamines with electrophiles is widely used for the synthesis of
α-alkylated carbonyl compounds, the direct use of an alcohol as an electrophile remains a problem in
organic transformations, due to the poor leaving ability of the hydroxyl unit and the decomposition of the
catalysts and active intermediates.
Recently, transition metal- or Lewis acid-catalyzed α-alkylation methods of carbonyl compounds using
alcohols have been developed [2-5]. Alternative approaches via the transition metal catalytic
dehydrogenation of alcohols has been described [6,7]. Furthermore, it is reported that a Lewis acid, such
as [IrCl(cod)]2 [8], InI3 [9], GaBr3 [9], La(OTf)3 [10] and Hf(OTf)3 [10], can be used as a catalyst for the
synthesis of α-alkyl substituted carbonyl compounds by the reaction of alcohols and enol acetates.
However, there are some drawbacks of these methods using alcohols as a carbon source; (i) limitation of
the substrates, (ii) instability of catalyst under a moist or air condition, (iii) the strong basic or acidic
conditions, and (iii) the use of small excess amounts of the reagent.
It was disclosed that a rhenium complex, such as ReX(CO)5 (X = Br and Cl), serves as an air and
moisture-tolerant catalyst for organic reactions instead of various Lewis acid catalysts [11,12]. Very
recently, our group has successfully demonstrated the rhenium-catalyzed coupling reaction of alcohols and
enol acetates [13,14]. In the continuation of this work, we wish to report the full details on the synthesis of
α-alkylated carbonyl compounds and γ,δ-unsaturated ketones by the rhenium complex-catalyzed coupling

reaction of various alkyl and allylic alcohols and enol acetates. In addition, we will show the results of the
ACCEPTED MANUSCRIPT
reaction of enol acetates and ethers instead of alcohols as the alkylated agent (Scheme 1).
R1 OH
cat.ReBr(CO)5
OAc
R3
O
R2
R1
+
R3
O
R1
R2
R1
Scheme 1.
2. Results and Discussion
Initially, we have chosen 1-phenylethanol (1a) and isopropenyl acetate (2a) as the model starting materials
to explore the optimized reaction conditions and investigated the effects of the rhenium complex catalyst,
reaction temperature, and solvent on the reaction (Table 1). When 1a was allowed to react with 2a in the
presence of a catalytic amount of ReBr(CO)5 (5 mol%) in a 1,2-dichloroethane solvent at 80 °C for 5 h, the
coupling reaction of 1a and 2a smoothly proceeded to give 4-phenyl-2-pentanone (3a) in 88% yield (entry
1). No reaction took place in the absence of the rhenium complex (entry 2) [15]. At the lower reaction
temperature (60 °C), the yield of 3a slightly decreased (entry 3). Even when toluene and THF were used as
the solvent, the reaction smoothly proceeded (entries 4 and 5). In the case of acetonitrile, 3a was not
formed at all (entry 6). The most promising reaction yield was obtained when the reaction was performed in
1,2-dichloroethane (entry 1). When ReCl(CO)5 was used instead of ReBr(CO)5 as the catalyst, 1a was
coupled with 2a to give 3a in 53% yield (entry 7). In the case of other rhenium complexes, such as
Re2(CO)10, Re2O7, ReCl5, and CH3ReO3, no formation of 3a was observed (entries 8-11).
Table 1. Reaction of 1-phenylethanol (1a) with isopropenyl acetate (2a)a
O
cat.Re complex
OAc
+
Ph
Ph OH
solvent
1a
2a
3a
entry
catalyst
solvent
temp (ºC) yield (%)b
1
2
3
4
ReBr(CO)5
none
CH2ClCH2Cl 80
CH2ClCH2Cl 80
CH2ClCH2Cl 60
88 (72)
0
ReBr(CO)5
ReBr(CO)5
52
58
toluene
80

5
ReBr(CO)5
ReBr(CO)5
ReCl(CO)5
Re2(CO)10
Re2O7
THF
80
56
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6
CH3CN
80
0
7
CH2ClCH2Cl 80
CH2ClCH2Cl 80
CH2ClCH2Cl 80
CH2ClCH2Cl 80
CH2ClCH2Cl 80
53
0
8c
9c
10
11
0
ReCl5
0
CH3ReO3
0
aReaction conditions: 1a (0.3 mmol), 2a (0.3 mmol), Re catalyst (5 mol%), solvent (2 mL), 5 h.
bGC yield. The number in parenthesis shows the isolated yield.
cRe catalyst (2.5 mol%).
Under the optimal reaction conditions, various alcohols were allowed to react with isopropenyl acetate
(2a) in the presence of a catalytic amount of ReBr(CO)5, and these results are shown in Table 2. The 1-aryl
substituted ethanols bearing electron-donating groups on the aromatic ring, such as 1-(4-methylphenyl)-
and 1-(4-methoxyphenyl)ethanol, gave the corresponding 4-aryl substituted 2-pentanones, 3b and 3c, in 84
and 80% yields, respectively (entries 2 and 3). The 1-(3-methylphenyl)- and 1-(2-methylphenyl)ethanol
produced the 4-(3-methylphenyl)- and 4-(2-methylphenyl)-2-pentanone, 3d,e, in 62 and 57% yields (entries
4 and 5). An electron withdrawing group, such as chlorine, substituted 1-aryl ethanol resulted in a
significant drop in the yield of the ketone 3f (entry 6). In the case of 1-(4-nitrophenyl)-1-ethanol, 3g was
not formed and 1-(4-nitrophenyl)ethyl acetate, which was a transesterficated product, was obtained in 82%
yield (entry 7). 4-Phenyl-2-hexanone, 4,4-diphenyl-2-butanone, and 4,4,4-triphenyl-2-butanone, 3h-j, were
also prepared by the coupling reaction between 1-phenyl-1-propanol, diphenylmethanol, or
triphenylmethanol and 2a (entries 8-10). The preparation of the 4-naphthyl substituted 2-pentanones, 3k,l,
was successfully achieved using the rhenium catalytic system (entries 11 and 12). Similarly,
4-methoxybenzyl
alcohol,
a
primary
alcohol,
was
coupled
with
2a
to
form
4-(4-methoxyphenyl)-2-butanone (3m) in 56% yield; however, in the case of benzyl alcohol,
4-phenyl-2-butanone, 3n, was not formed at all (entries 13 and 14).

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Table 2. Reaction of alcohols 1 with isopropenyl acetate (2a)a
R1
R1
O
OAc
cat.ReBr(CO)5
CH2ClCH2Cl
R2 OH
+
R2
1
2a
3
entry
alcohol
yield (%)b
OH
X
1
2
3
4
5
6
7
X = H (1a)
72 (3a)
84 (3b)
80 (3c)
62 (3d)
57 (3e)
38 (3f)
0 (3g)
X = 4-CH3 (1b)
X = 4-CH3O (1c)
X = 3-CH3 (1d)
X = 2-CH3 (1e)
X = 4-Cl (1f)
X = 4-NO2 (1g)
R
Ph OH
8
R = C2H5 (1h)
R = Ph (1i)
Ph
29 (3h)
83 (3i)
78 (3j)
9
10
(1j)
Ph OH
Ph
11
12
63 (3k)
63 (3l)
(1k)
OH
(1l)
OH
13
56 (3m)
OH
(1m)
CH3O

14
0 (3n)
ACCEPTED MANUSCRIPT
OH
(1n)
aReaction conditions: alcohol 1 (0.3 mmol), 2a (0.3 mmol), ReBr(CO)5 (5 mol%), CH2ClCH2Cl (2 mL),
at 80 ºC for 5 h. bIsolated yield.
Next, 1-phenylethanol (1a) was treated with various types of enol acetates, and these results are shown in
Table 3. The yields of the products from the reaction of 1a and enol acetates derived from acetophenones
with the electron withdrawing group were higher than those of the reaction with the electron donating
group substituted ones (entries 1-5). 2-(1-Phenylethyl)cyclohexanone (4g) was also formed by the reaction
of 1a and cyclohexenyl acetate 2g (entry 6). Similarly, the enol acetate 2h, which was prepared from an
aldehyde, gave the corresponding α-alkylated aldehyde 4h (entry 7). The treatment of 1a and the mixture of
E- and Z-isomers 2i (E/Z = 1.5/1.0) gave a mixture of regioisomers 4i (syn/anti = 1.0/1.5). It is interesting
to note that when the mixture of the E- and Z-isomers 2i (E/Z = 1.0/7.2) was used as the enol acetate, the
distribution of products 4i (syn/anti = 1.0/1.3) was almost the same (entries 8 and 9).
Table 3. Reaction of 1-phenylethanol (1a) with enol acetates 2a
O
cat.ReBr(CO)5
OAc
R2
R1
+
Ph
Ph OH
1a
R2
CH2ClCH2Cl
R1
4
2
entry
enol acetate
yield (%)b
OAc
X
1
2
3
4
5
6
X = H (2b)
57 (4b)
48 (4c)
9 (4d)
X = 4-CH3 (2c)
X = 4-CH3O (2d)
X = 4-Cl (2e)
81 (4e)
65 (4f)
58 (4g)
X = 4-NO2 (2f)
OAc
(2g)
7
32 (4h)
(2h)
OAc

n-C10H21
ACCEPTED MANUSCRIPT
OAc
8
9
43c (4i)
E / Z = 1.5 / 1.0
E / Z = 1.0 / 7.2
23d (4i)
aReaction conditions: 1a (0.2 mmol), enol acetate 2 (0.4 mmol), ReBr(CO)5 (5 mol%), CH2ClCH2Cl (5
mL), at 80 ºC for 5 h.
bIsolated yield.
cSyn / anti = 1.0 / 1.5
dSyn / anti = 1.0 / 1.3
In order to determine the possibility of the synthesis of γ,δ-unsaturated ketones by the rhenium-catalyzed
coupling reaction of the allylic alcohols and isopropenyl acetate (2a), various allylic alcohols 5 were treated
with 2a in the presence of a catalytic amount ReBr(CO)5, and these results are shown in Table 4. When
1,3-diphenyl-1-propene-3-ol (5a) was reacted with one equivalent amount of 2a in the presence of
ReBr(CO)5 catalyst, (E)-4,6-diphenyl-5-hexene-2-one (6a), the γ,δ-unsaturated ketone, was formed in 46%
yield. The yield of 6a was improved by using two equivalent amounts of 2a (entry 1). The 1,3-diaryl
substituted allylic alcohols bearing a methyl group on the both aromatic rings, 1,3-di(4-methylphenyl)-,
1,3-di(3-methylphenyl)-, and 1,3-di(2-methylphenyl)-1-propene-3-ol, 5b-d, gave the corresponding
(E)-4,6-diaryl-5-hexene-2-ones, 6b-d, in 82, 73, and 70% yield, respectively (entries 2-4). The introduction
of a methoxy group on both aromatic rings caused a decrease in the yield of the γ,δ-unsaturated carbonyl
compound, 6e, due to the preparation of various by-products (entry 5). For the reaction of
1,3-di(4-chlorophenyl)-1-propene-3-ol (5f), which has an electron withdrawing group on both aromatic
rings, di(4-chlorophenyl)-5-hexene-2-one (6f) was formed in 90% yield (entry 6). Similarly, the cyclic
allylic alcohol, such as cyclohexene-3-ol (5g), coupled with 2a to give 1-(cyclohex-2-enyl)-2-propanone
(6g) in 45% yield (entry 7). Similarly, 1,3-diphenylprop-1-en-3-ol (4a) was coupled with various enol
acetals to give the corresponding γ,δ-unsaturated ketones in 83-93 % yields (Table 5).
Table 4. Reaction of allylic alcohols 5 with isopropenyl acetate (2a)a
O
cat.ReBr(CO)5
OH
OAc
+
R
R
CH2ClCH2Cl
R
R
5
2a
6

entry
alcohol
yieldb (%)
ACCEPTED MANUSCRIPT
1
2
3
4
5
6
7
R = Ph (5a)
96 (6a)
82 (6b)
73 (6c)
70 (6d)
18 (6e)
90 (6f)
45 (6g)
R = 4-CH3C6H4 (5b)
R = 3-CH3C6H4 (5c)
R = 2-CH3C6H4 (5d)
R = 4-CH3OC6H4 (5e)
R = 4-ClC6H4 (5f)
(5g)
OH
aReaction conditions: alcohol 5 (0.2 mmol), 2a (0.4 mmol), ReBr(CO)5 (5 mol%), CH2ClCH2Cl (5 mL),
at 80 ºC for 5 h.
bIsolated yield.
Table 5. Reaction of 1,3-diphenyl-1-propene-3-ol- (5a) with enol acetates 2a
O
cat.ReBr(CO)5
OH
Ar
Ph
OAc
Ar
+
Ph
Ph
Ph
CH2ClCH2Cl
5a
2
6
entry
enol acetate
yield (%)b
93 (6h)
89 (6i)
1
2
3
4
5
Ar = Ph (2b)
Ar = 4-CH3C6H4 (2c)
Ar = 4-CH3OC6H4 (2d)
Ar = 4-ClC6H4 (2e)
83 (6j)
91 (6k)
85 (6l)
Ar = 4-NO2C6H4 (2f)
aReaction conditions: 5a (0.2 mmol), enol acetate 2 (0.4 mmol), ReBr(CO)5 (5 mol%), CH2ClCH2Cl (5
mL), at 80 ºC for 5 h.
bIsolated yield.
Next, the reaction of 1,3-diaryl substituted allylic alcohols, in which two different aryl groups were
substituted at the C1 and C3 positions of the allyl alcohol, and 2a was investigated (Scheme 2). When
3-(4-methylphenyl)-1-phenyl-1-propene-3-ol (7a) was used as an allylic alcohol, γ,δ-unsaturated ketones

were formed in 60% yield with the mixture of (E)-4-(4-methylphenyl)-6-phenyl-5-hexene-2-one (8a) and
ACCEPTED MANUSCRIPT
(E)-6-(4-methylphenyl)-4-phenyl-5-hexene-2-one (8a’) (8a : 8a’ = 1.6 : 1.0). For the reaction of
1-(4-methylphenyl)-3-phenyl-1-propene-3-ol (7b), the coupling products, 8a and 8a’, were obtained with
almost same ratio as that of the reaction of 7a. The reaction of various 1,3-diaryl substituted allylic alcohols
bearing different two aryl moieties also gave a mixture of 4,6-diaryl substituted 5-hexene-2-ones. It is
interesting to note that the distribution of the two isomers was almost the same for the various 1,3-diaryl
substituted allylic alcohols. It was found that the carbon-carbon bond formation was preferentially occurred
at the carbon adjacent to the electron rich aryl group. For the reaction of 1-aryl-2-butene-1-ol and
1-aryl-1-butene-3-ol, in which aryl and methyl groups are substituted on the allyl alcohol, 2a was
predominantly coupled at the carbon adjacent to the methyl group.
In order to determine the reasons for the preparation of the mixture of two isomers by the reaction of
1,3-diaryl
substituted
allylic
alcohols
bearing
different
aryl
groups,
3-(4-methylphenyl)-1-phenyl-1-propene-3-ol (7a) or 1-(4-methylphenyl)-3-phenyl-1-propene-3-ol (7b) was
1
treated with the ReBr(CO)5 catalyst at 80 ºC, and the reaction was monitored by their H-NMR spectra.
Within 10 min, the isomerization of the allylic alcohols by the 1,3-transposition of the hydroxyl group was
observed and the mixture of 7a and 7b was formed.[16] Based on these results, it was suggested that
isomerization of allylic alcohol by the 1,3-transposition of the hydroxyl group easily occurred in the
presence of ReBr(CO)5 to form the mixture of allylic alcohols.

OH
OAc
ACCEPTED MANUSCRIPT
O
+
O
cat.ReBr(CO)5 (5 mol%)
+
2a (0.4 mmol)
7a (0.2 mmol)
CH2ClCH2Cl (5 ml)
80 oC, 5h
OH
8a
8a'
+
2a
60% (8a : 8a'= 1.6 : 1.0)
62% (8a : 8a' = 1.6 : 10.)
(0.4 mmol)
7b (0.2 mmol)
OH
OAc
O
+
O
cat.ReBr(CO)5 (5 mol%)
O
O
+
2a (0.4 mmol)
7c (0.2 mmol)
O
O
CH2ClCH2Cl (5 ml)
OH
80 oC, 5h
8b
8b'
+
2a
34% (8b: 8b' = 3.0 : 1.0)
35% (8b : 8b'= 3.1 : 1.0)
(0.4 mmol)
OAc
7d (0.2 mmol)
OH
O
+
O
cat.ReBr(CO)5 (5 mol%)
Cl
+
2a (0.4 mmol)
7e (0.2 mmol)
Cl
Cl
CH2ClCH2Cl (5 ml)
OH
80 oC, 5h
8c
8c'
+
2a
74% (8c : 8c' = 1.0 : 1.8)
73% (8c : 8c' = 1.0 : 1.8)
Cl
(0.4 mmol)
OAc
7f (0.2 mmol)
OH
O
+
O
cat.ReBr(CO)5 (5 mol%)
Cl
Cl
+
2a (0.4 mmol)
7g (0.2 mmol)
Cl
Cl
CH2ClCH2Cl (5 ml)
OH
80 oC, 5h
8d
8d'
+
2a
72% (8d : 8d' = 1.0 : 2.0)
74% (8d : 8d' = 1.0 : 2.0)
(0.4 mmol)
OAc
7h (0.2 mmol)
OH
O
+
O
cat.ReBr(CO)5 (5 mol%)
+
2a (0.8 mmol)
7i (0.2 mmol)
CH2ClCH2Cl (5 ml)
80 oC, 5h
OH
8e
8e'
+
2a
76% (8e : 8e' = 1.0 : 2.1)
75% (8e : 8e' = 1.0 : 2.3)
(0.8 mmol)
7j (0.2 mmol)

ACCEPTED MANUSCRIPT
OH
2a
+
O
O
ReBr(CO)5 (5 mol%)
7k (0.2 mmol)
(0.8 mmol)
+
CH2ClCH2Cl (5 mL)
80 oC, 5 h
OH
2a
+
8f
8f'
69% (8f : 8f' = 1.0 : 1.8)
7l (0.2 mmol)
(0.8 mmol)
67% (8f : 8f' = 1.0 : 1.8)
OH
+
2a
O
O
Cl
Cl
ReBr(CO)5 (5 mol%)
7m 0.2 mmol)
(0.8 mmol)
+
CH2ClCH2Cl (5 mL)
80 oC, 5 h
OH
Cl
+
2a
Cl
8g
8g'
84% (8g : 8g' = 1.0 : 4.2)
7n (0.2 mmol)
(0.8 mmol)
81% (8g : 8g' = 1.0 : 4.2)
Scheme 2
To obtain the information about the reaction pathway, the time-dependence of the products was followed
by GC measurement at the appropriate time intervals (Fig. 1). The GC analysis of the reaction products
showed that di(1-phenylethyl) ether (9a) was formed as the main product at an early stage of the
reaction.[17] The yield of 9a then gradually decreased and the yields of 3a and α-methylbenzyl acetate
(10a) increased. The acetate 10a was gradually converted into 3a. In fact, when di(1-phenylethyl) ether
(9a) (0.3 mmol) was treated with two equivalent amounts of 2a (0.6 mmol) in the presence of the
ReBr(CO)5 catalyst, 4-phenyl-2-pentanone (3a) was formed in 77% yield (0.47 mmol) (Scheme 3). The
conversion of 10a into 3a was also achieved by the rhenium catalyst. Based on these results, it was
suggested that both 9a and 10a were intermediates during the coupling reaction. On the other hand, in the
case of 1,3-diphenyl-1-propen-3-ol, the intermolecular dehydration product was not observed on the
time-dependence of the products

ACCEPTED MANUSCRIPT
Figure 1. Time-dependence curves for the Re-catalyzed reaction of 1a (0.3 mmol) with 2a (0.3 mmol) in
CH2ClCH2Cl (2 mL) at 80 ºC for 6 h
cat.ReBr(CO)5 (5 mol%)
+
2a
3a
Ph
O
Ph
CH2ClCH2Cl (5 ml)
80 °C, 5h
77%
(0.6 mmol)
9a (0.3 mmol)
(0.47 mmol)
O
cat.ReBr(CO)5 (5 mol%)
+
2a
3a
Ph
O
CH2ClCH2Cl (5 ml)
80 °C, 5h
85%
(0.3 mmol)
10a (0.3 mmol)
(0.25 mmol)
Scheme 3.
Based on the above observations, the plausible reaction pathways for the rhenium-catalyzed reaction are
shown in Scheme 4 and 5. First, 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 [18]. In the case of
1-phenyl-1-ethanol 1a, the C-O bond of di(phenylethyl) ether (9a), which is in situ formed by the
intermolecular dehydration of 1a, is activated by coordinating of the rhenium species to increase the
positive charge on the α-methylbenzyl group. The addition of the activated coordinating rhenium species to
the C=C double bond of enol acetate 2a followed by the deacetoxylation then gave the corresponding
ketone 3a and α-methylbenzyl acetate (10a) [19]. The reaction of 10a with 1a easily occurred in the
presence of the rhenium catalyst to afford 3a.
On the other hand, in the case of
1,3-diphenyl1-propen-3-ol, the coordinating of the rhenium species to the oxygen atom of allylic alcohol
followed by the C-O bond cleavage of alcohol to form the corresponding allylic cation. The reaction of
cation with 2a easily occurred to afford the corresponding γ,δ-unsaturated carbonyl compounds 3.

ReBr(CO)5
ACCEPTED MANUSCRIPT
O
O
-
+ CO
CO/∆
+
Ph
Ph
O
ReBr(CO)4
Ph OH
10a
3a
1a
H2O
OReBr(CO)4
Ph
O
Ph
Ph
OAc
ReBr(CO)4
Ph
OAc
OReBr(CO)4
Ph
2a
Scheme 4.
O
ReBr(CO)5
-
+ CO
CO/∆
+
AcOH
ReBr(CO)4
R
R
OH
6
R
R
5
(HO)ReBr(CO)4
OAc
ReBr(CO)4
OH
R
R
R
R
OAc
2a
R
R
(HO)ReBr(CO)4
Scheme 5.
Based on the result of the reaction of bis(1-phenylethyl) ether (9a) with isopropenyl acetate (2a) shown in
Scheme 3, it is suggested that both alkyl groups of the ether were efficiently used for the synthesis of the

α-alkylated ketones by the reaction of ethers and enol acetates. We then investigated the use of ether as a
ACCEPTED MANUSCRIPT
carbon source for the synthesis of ketones by the reaction of isopropenyl acetate (2a) (Scheme 6). When
bis[1-(4-methoxyphenyl)ethyl] ether was allowed to react with 1a, both 1-(4-methoxyphenyl)ethyl groups
were also introduced to 1a and 2-(4-methoxyphenyl)-2-pentanone was formed in 0.38 mmol (63% based on
2a). In the case of bis(diphenylmethyl) ether, the corresponding ketone was formed in good yield. On the
other hand, when di(4-methoxyphenylmethyl)ether was used as an alkylated reagent, the yield of the ketone
was low.
cat.ReBr(CO)5 (5 mol%)
3c
2a
O
+
CH2ClCH2Cl (5 ml)
80 °C, 5h
O
O
(0.38 mmol)
(0.3 mmol)
(0.6 mmol)
cat.ReBr(CO)5 (5 mol%)
Ph Ph
3i
2a
+
Ph
O
Ph
CH2ClCH2Cl (5 ml)
80 °C, 5h
(0.49 mmol)
(0.3 mmol)
(0.6 mmol)
cat.ReBr(CO)5 (5 mol%)
3m
2a
O
+
CH2ClCH2Cl (5 ml)
80 °C, 5h
O
O
(0.23 mmol)
(0.3 mmol)
(0.6 mmol)
Scheme 6.
3. Conclusion
In summary, we have now developed a novel catalytic ability of the rhenium complex for the
carbon-carbon formation of alcohols and enol acetates giving the corresponding carbonyl and
γ,δ-unsaturated carbonyl compounds. Furthermore, for the rhenium-catalyzed system, ethers were also
utilized as the alkylated source. In particular, in the case of ethers, both alkyl units of the ethers were
utilized on the reaction.
4. Experimental section
4.1. General

FT-IR spectra were recorded on a JASCO FT/IR-4100 instrument. 1H-NMR spectra were recorded at 400
ACCEPTED MANUSCRIPT
MHz and 13C-NMR spectra at 100 MHz on JEOL a JNM-ECS-400 or a JEOL JNM-AL400. Chemical
shifts were reported in ppm relative to tetramethylsilane or residual solvent as the internal standard. GLC
mass spectral analyses were performed on a Shimadozu GCMS-QP5050A with CBP-M25-025. High mass
spectral analyses were performed on a JEOL JMS-T200GC and 7890B GC with HP-5 system. Preparative
HPLC separation was undertaken with a JAI LC-908 chromatograph using 600 mm X 20 mm JAIGEL-1H
and 2H GPC columns with CHCl3 as an eluent. ReBr(CO)5, ReCl(CO)5, MeReO3, Re2(CO)10, ReCl5 and
Re2O7 were commercially available and were used without further purification. Alcohols (1a-1h, 1k, and
1l) and allyl alcohols were prepared by the reduction of the corresponding ketones and α,β-unsaturated
carbonyl compounds. α,β-Unsaturated carbonyl compounds were prepared by the Aldol condensation of
corresponding ketones and aldehydes. Enol acetates (2a-2g) were prepared by the reaction of the
corresponding ketones and 1a. Enol acetal (2i) was prepared by the reaction of the corresponding aldehyde
and acetic acid anhydride. Other chemical agents were obtained commercially and were purified if
necessary by distillation.
4.2. Procedure
4.2.1. General procedure for rhenium-catalyzed reaction of alcohol 1 with enol acetate 2
A 1,2-dichloroethane (2.0 mL) solution of alcohol 1 (0.3 mmol), enol acetate 2 (0.3 mmol), and ReBr(CO)5
(5 mol%) was stirred under an atmosphere of nitrogen at 80 ºC for 5 h. After the reaction was complete,
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 carbonyl compounds. Further purification was carried out by
recyclable preparative HPLC, if necessary. The structures of the products were assigned by their 1H and
13C-NMR, and mass spectra. The product was characterized by comparing its spectral data with those of
authentic sample or previous reports 3a [20], 3b [21], 3c [21a], 3e [22], 3f [21a, 23], 3h [24], 3i [25], 3j
[26], 3k [22], 3l [27], 3m [28], 4b [24], 4d [29], 4g [21a,30], 4h [31], 6a [32], 6g [21a], 6h [33], 8e [34],
and 8e’ [35]. The structures of the products (3d, 4c, 4e, 4f, 4i, 6b, 6c, 6d, 6e, 6f, 6i, 6j, 6k, 6l, 8a, 8a’, 8b,
8b’, 8c, 8c’, 8d, 8d’, 8f, 8f’, 8g, and 8g’) were assigned by their 1H and 13C NMR, IR, and high resolution
mass spectra analysis.
4.2.2. Procedure for rhenium-catalyzed reaction of isopropenyl acetate (2a) with ether in
Scheme6
A 1,2-dichloroethane (2.0 mL) solution of isopropenyl acetate (2a) (0.6 mmol), corresponding ether (0.3
mmol) and ReBr(CO)5 (5 mol%) was stirred under an atmosphere of nitrogen at 80 ºC for 5 h. After the

reaction was complete, H O was added to the reaction mixture and extracted with ethyl acetate. The organic
ACCEPTED MANUSCRIPT
2
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 the corresponding ketone 3. The
product was characterized by comparing its spectral data with those of authentic sample. The product was
characterized by comparing its spectral data with those of authentic sample or previous reports 3a [20], 3c
[21a], 3i [24], and 3m [28].
4.2.3. Procedure for rhenium-catalyzed reaction of isopropenyl acetate (2a) with
1-phenylethyl acetate (10a)
A 1,2-dichloroethane (2.0 mL) solution of isopropenyl acetate (2a) (0.3 mmol), 1-phenylethyl acetate (10a)
(0.3 mmol) and ReBr(CO)5 was stirred under an atmosphere of nitrogen at 80 ºC for 5 h. After the reaction
was complete, 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 4-phenylpentan-2-one (3a). The product (3a) was
characterized by comparing its spectral data with those of authentic sample [20].
1
3d: H-NMR (400 MHz, CDCl3) δ 1.26 (d, J = 6.8 Hz, 3H), 2.07 (s, 3H), 2.34 (s, 3H), 2.65 (dd, J = 16.0,
8.0 Hz, 1H), 2.75 (dd, J = 16.4, 6.4 Hz, 1H), 3.27 (ddq, J = 6.8, 8.0, 6.4 Hz, 1H), 6.83-7.02 (m, 3H), 7.19 (t,
13
J = 7.6 Hz, 1H). C-NMR (100 MHz, CDCl3) δ 21.4, 22.0, 30.5, 35.4, 52.0, 123.7, 127.0, 127.5, 128.4,
138.0, 146.1, 207.9. IR (KBr) 704, 784, 1159, 1268, 1360, 1606, 1718, 2872, 2926, 2961 cm-1. MS: m/z
Calcd. for C12H16O: 176.1201; Found: 176.1193.
1
4c: H-NMR (400 MHz, CDCl3) δ 1.33 (d, J = 6.8 Hz, 3H), 2.40 (s, 3H), 3.15 (dd, J = 16.0, 8.4 Hz, 1H),
3.26 (dd, J = 16.0, 5.6 Hz, 1H), 3.49 (ddq, J = 6.8, 8.4, 5.6 Hz, 1H), 7.17-7.32 (m, 7H), 7.83 (d, J = 8.4 Hz,
2H). 13C-NMR (100 MHz, CDCl3) δ 21.6, 21.8, 35.6, 46.9, 126.2, 126.8, 128.2, 128.5, 129.2, 134.7, 143.7,
146.7, 198.7. IR (KBr) 700, 761, 808, 1180, 1269, 1407, 1452, 1606, 1683, 2925, 2963, 3028 cm-1. MS:
m/z Calcd. for C17H18O: 238.1358; Found: 238.1348.
1
4e: H-NMR (400 MHz, CDCl3) δ 1.34 (d, J = 6.8 Hz, 3H), 3.15 (dd, J = 16.4, 8.0 Hz, 1H), 3.27 (dd, J =
16.4, 5.6 Hz, 1H), 3.49 (ddq, J = 6.8, 8.0, 5.6 Hz, 1H), 7.18-7.32 (m, 5H), 7.41 and 7.85 (AA’BB’, JAB
=
8.8 Hz, 4H). 13C-NMR (100 MHz, CDCl3) δ 21.8, 35.5, 46.9, 126.3, 126.8, 128.5, 128.8, 129.5, 135.4,
139.4, 146.3, 197.8. IR (KBr) 700, 760, 817, 990, 1092, 1201, 1270, 1399, 1589, 1687, 1945, 2927, 2964,
3028, 3061 cm-1. MS (EI): 258 (M+). Calcd for C16H15ClO, 258.0811; Found 258.0835.
1
4f: H-NMR (400 MHz, CDCl3) δ 1.37 (d, J = 7.2 Hz, 3H), 3.22 (dd, J = 16.8, 7.6 Hz, 1H), 3.35 (dd, J =
16.8, 6.0 Hz, 1H), 3.50 (ddq, J = 7.2, 7.6, 6.0 Hz, 1H), 7.15-7.32 (m, 5H), 8.03 and 8.28 (AA’BB’, JAB
=
8.4 Hz, 4H). 13C-NMR (100 MHz, CDCl3) δ 21.9, 35.6, 47.5, 123.8, 126.5, 126.8, 128.6, 129.0, 141.5,
145.8, 150.2, 197.5. IR (KBr) 701, 744, 764, 855, 1197, 1318, 1346, 1525, 1604, 1693, 2928, 2964, 3028,
3082, 3107cm-1. MS (EI): 269 (M+). Calcd for C16H15NO3, 269.1052; Found 269.1083.

4i (mixture of isomers: syn/anti = 1.0/1.5): 1H-NMR (400 MHz, CDCl ) δ 0.85-0.89 (m, 3H), 1.15-1.32 (m,
ACCEPTED MANUSCRIPT3
19H), 1.41-1.63 (m, 2H), 2.42-2.46 (m, 1H), 2.96 (dt, J = 16.8, 7.2 Hz, 0.56H), 3.09 (quint, J = 7.2 Hz,
0.44H), 7.15-7.34 (m, 5H), 9.48 (d, J = 3.2 Hz, 0.44 H), 9.59 (d, J = 4.0 Hz, 0.56H). 13C-NMR (100 MHz,
CDCl3) δ 14.1, 18.5, 18.6, 20.3, 20.9, 22.7, 26.7, 27.1, 27.3, 27.8, 29.28, 29.33, 29.38, 29.43, 29.52, 29.54,
29.59, 29.63, 29.7, 31.9, 40.00, 40.02, 41.9, 52.8, 58.0, 58.6, 126.5, 126.6, 127.4, 127.5, 128.5, 128.6,
143.9, 144.0, 205.3, 205.5. IR (KBr) 700, 763, 1726, 2854, 2925, 3029 cm-1. MS (EI): 288 (M+). Calcd for
C20H32O, 288.2453; Found C, 288.2435.
6b: 1H-NMR (400 MHz, CDCl3) δ 2.09 (s, 3H), 2.30 (s, 3H), 2.31 (s, 3H), 2.85-2.96 (m, 2H), 4.05-4.10 (m,
13
1H), 6.24 (dd, J = 16.0, 6.8 Hz, 1H), 6.33 (d, J = 16.0 Hz, 1H), 7.06-7.23 (m, 8H). C-NMR (100 MHz,
CDCl3) δ 21.0, 21.1, 30.7, 43.6, 49.5, 126.1, 127.4, 129.1, 129.3, 129.6, 131.5, 134.3, 136.1, 137.0, 140.0,
207.2. IR (KBr) 668, 794, 967, 1158, 1356, 1416, 1513, 1716, 2922, 3024 cm-1. MS: m/z Calcd. for
C20H22O: 278.1671; Found: 278.1678.
6c: 1H-NMR (400 MHz, CDCl3) δ 2.09 (s, 3H), 2.30 (s, 3H), 2.33 (s, 3H), 2.86-2.97 (m, 2H), 4.00-4.05 (m,
1H), 6.28 (dd, J = 16.0, 6.0 Hz, 1H), 6.35 (d, J = 16.0 Hz, 1H), 6.99-7.06 (m, 4H), 7.11-7.22 (m, 4H).
13C-NMR (100 MHz, CDCl3) δ 21.3, 21.4, 30.7, 43.9, 49.3, 123.4, 124.5, 126.8, 127.4, 128.0, 128.3, 128.4,
128.5, 129.8, 132.2, 137.0, 137.9, 138.2, 142.9, 207.0. IR (KBr) 694, 774, 964, 1159, 1359, 1489, 1604,
1717, 2920, 3026 cm-1. MS: m/z Calcd. for C20H22O: 278.1671; Found: 278.1670.
6d: 1H-NMR (400 MHz, CDCl3) δ 2.12 (s, 3H), 2.25 (s, 3H), 2.42 (s, 3H), 2.88-3.01 (m, 2H), 4.33 (q, J =
7.2 Hz, 1H), 6.10 (dd, J = 16.0, 7.6 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 7.09-7.21 (m, 7H), 7.32-7.34 (m,
1H). 13C-NMR (100 MHz, CDCl3) δ 19.6, 19.7, 30.7, 39.6, 48.9, 125.5, 125.9, 126.1, 126.2, 126.4, 127.1,
127.9, 130.1, 130.6, 133.3, 135.1, 135.9, 136.3, 140.9, 207.0. IR (KBr) 749, 966, 1158, 1355, 1460, 1489,
1601, 1653, 1718, 2922, 3019 cm-1. MS: m/z Calcd. for C20H22O: 278.1671; Found: 278.1681.
1
6e: H-NMR (400 MHz, CDCl3) δ 2.10 (s, 3H), 2.84-2.95 (m, 2H), 3.19 (s, 6H), 4.00 (q, J = 7.2 Hz, 1H),
6.16 (dd, J = 16, 6.8 Hz, 1H), 6.29 (d, J = 8.4 Hz, 1H), 6.83 (q, J = 8.4 Hz, 4H), 7.17 (d, J = 8.8 Hz, 2H),
13
7.25 (d, J = 8.8 Hz, 2H). C-NMR (100 MHz, CDCl3) δ 30.4, 42.9, 49.3, 54.9, 55.0, 113.6, 113.7, 127.1,
128.3, 128.7, 129.6, 130.3, 134.9, 158.0, 158.7, 206.9. IR (KBr) 523, 546, 832, 967, 1033, 1112, 1175,
1249, 1301, 1357, 1418, 1422, 1464, 1510, 1608, 1700, 1716, 2835, 2957, 2999 cm-1. MS: m/z Calcd. for
C20H22O3: 310.1569; Found: 310.1550.
6f: 1H-NMR (400 MHz, CDCl3) δ 2.11 (s, 3H), 2.87-2.98 (m, 2H), 4.05 (dd, J = 16, 7.4 Hz, 1H), 6.22-6.32
13
(m, 2H), 7.16-7.31 (m, 8H). C-NMR (100 MHz, CDCl3) δ 30.4, 42.8, 48.8, 127.3, 128.4, 128.6, 128.8,
128.9, 132.2, 132.4, 132.8, 135.3, 141.0, 206.0. IR (KBr) 504, 539, 667, 670, 720, 827, 967, 1013, 1092,
1158, 1232, 1359, 1405, 1491, 1593, 1699, 1718, 1897, 2891, 3028 cm-1. MS: m/z Calcd. for C18H16Cl2O:
318.0578; Found: 318.0562.

6i: 1H-NMR (400 MHz, CDCl ) δ 2.38 (s, 3H), 3.40-3.52 (m, 2H), 4.27-4.32 (m, 1H), 6.35-6.44 (m, 2H),
ACCEPTED MANUSCRIPT
3
7.14-7.32 (m, 10H), 7.84 (d, J = 8.4 Hz, 2H). 13C-NMR (100 MHz, CDCl3) δ 21.6, 43.9, 44.3, 126.2, 126.5,
127.2, 127.7, 128.2, 128.4, 128.6, 129.2, 130.0, 132.7, 134.6, 137.2, 143.3, 143.8, 197.7. IR (KBr) 697,
744, 809, 965, 1180, 1493, 1606, 1685, 3027 cm-1. MS: m/z Calcd. for C24H22O: 326.1671; Found:
326.1675.
6j: 1H-NMR (400 MHz, CDCl3) δ 3.39-3.49 (m, 2H), 3.83 (s, 3H), 4.26-4.32 (m, 1H), 6.35-6.45 (m, 2H),
6.89-6.91 (m, 2H), 7.14-7.31 (m, 10H), 7.92 (d, J = 8.4 Hz, 2H). 13C-NMR (100 MHz, CDCl3) δ 44.0, 44.1,
55.4, 113.7, 126.2, 126.5, 127.1, 127.7, 127.7, 128.4, 128.6, 129.9, 130.2, 130.3, 132.7, 137.2, 143.4,
163.4, 196.6. IR (KBr) 801, 947, 1074, 1205, 1505, 1963, 2570, 2889, 3026 cm-1. m.p. 114-115 ºC. MS:
m/z Calcd. for C24H22O2: 342.1620; Found: 342.1617.
6k: 1H-NMR (400 MHz, CDCl3) δ 3.44 (dd, J = 6.4, 2.8 Hz, 2H), 4.24-4.30 (m, 1H), 6.39 (t, J = 2.0 Hz,
2H), 7.15-7.31 (m, 10H), 7.39 (d, J = 8.8 Hz, 2H), 7.85 (d, J = 9.2 Hz, 2H). 13C-NMR (100 MHz, CDCl3) δ
43.9, 44.3, 126.1, 126.6, 127.2, 127.6, 128.4, 128.6, 128.8, 129.4, 130.1, 132.3, 135.3, 137.0, 139.4, 143.0,
196.8. IR (KBr) 698, 745, 818, 967, 1087, 1196, 1396, 1447, 1487, 1588, 1685, 3025, 3054 cm-1. MS: m/z
Calcd. for C23H19ClO: 346.1124; Found: 346.1127.
6l: 1H-NMR (400 MHz, CDCl3) δ 3.53 (d, J = 7.2 Hz, 2H), 4.25-4.30 (m, 1H), 6.40 (t, J = 2.0 Hz, 2H),
7.17-7.32 (m, 10H), 8.04 (m, J = 8.8 Hz, 2H), 8.26 (d, J = 8.8 Hz, 2H). 13C-NMR (100 MHz, CDCl3) δ 43.9,
45.0, 123.8, 126.2, 126.8, 127.4, 127.6, 128.4, 128.7, 129.0, 130.4, 131.8, 136.8, 141.4, 142.6, 150.2, 196.7.
IR (KBr) 700, 745, 987, 1227, 1348, 1452, 1598, 1700, 3024 cm-1. m.p. 99-100 ºC. MS: m/z Calcd. for
C23H19NO3: 357.1364; Found: 357.1371.
1
Mixture of 8a and 8a’ (8a : 8a’ = 1.6：1.0): H-NMR (400 MHz, CDCl3) δ 2.09 (s, 3H), 2.30 (s, 1.2H),
2.31 (s, 1.8H), 2.86-2.97 (m, 2H), 4.01-4.08 (m, 1H), 6.23-6.39 (m, 2H), 7.06–7.32 (m, 9H). 13C-NMR (100
MHz, CDCl3) δ 21.0, 21.1, 30.7, 43.5, 43.9, 49.4, 126.1, 126.2, 126.6, 127.2, 127.4, 127.6, 128.4, 128.6,
129.1, 129.3, 129.6, 129.7, 131.2, 132.5, 134.2, 136.2, 137.0, 137.1, 139.8, 143.0, 206.9, 207.0. IR (KBr)
700, 802, 1018, 1262, 1356, 1513, 1718, 2927, 3025 cm-1. MS: m/z Calcd. for C19H20O: 264.1514; Found:
264.1509, 264.1511.
1
Mixture of 8b and 8b’ (8b : 8b’ = 3.1：1.0): H-NMR (400 MHz, CDCl3) δ 2.10 (s, 3H), 2.86-2.99 (m,
2H), 3.79 (s, 3H), 4.08-4.00 (m, 1H), 6.17 (dd, J = 16.0, 7.2 Hz, 2H), 6.27-6.37 (m, 1.7H), 6.83 (dd, J =
13
16.0, 8.8 Hz, 2H), 7.16-7.32 (m, 8H). C-NMR (100 MHz, CDCl3) δ 29.6, 30.6, 30.7, 43.1, 43.9, 49.5,
55.1, 55.2, 113.8, 114.0, 126.2, 126.6, 127.2, 127.3, 127.6, 128.4, 128.5, 128.6, 129.3, 129.6, 129.8, 130.1,
132.6, 134.8, 137.1, 143.1, 158.2, 159.0, 207.0, 207.1. IR (KBr) 694, 753, 829, 966, 1033, 1111, 1158,
1176, 1251, 1301, 1359, 1419, 1450, 1464, 1608, 1716, 2852, 2924, 3033 cm-1. MS: m/z Calcd. for
C19H20O2: 280.1463; Found: 280.1460, 280.1459.

1
ACCEPTED MANUSCRIPT
Mixture of 8c and 8c’ (8c : 8c’ = 1.0：1.8): H-NMR (400 MHz, CDCl3) δ 2.10 (s, 3H), 2.86-2.99 (m, 2H),
4.05-4.12 (m, 1H), 6.24-6.37 (m, 2H), 7.17-7.33 (m, 9H). 13C-NMR (100 MHz, CDCl3) δ 29.6, 30.7, 43.0,
43.8, 49.1, 49.2, 126.2, 126.7, 127.3, 127.4, 127.6, 128.4, 128.5, 128.6, 128.7, 129.0, 130.2, 131.7, 132.3,
132.8, 133.0, 135.5, 136.8, 141.4, 142.6, 206.4, 206.7. IR (KBr) 700, 750, 822, 965, 1012, 1091, 1158,
1357, 1405, 1452, 1491, 1599, 1718, 3026, 3058 cm-1. MS: m/z Calcd. for C18H17ClO: 284.0968; Found:
284.0960.d
Mixture of 8d and 8d’ (8d : 8d’ = 1.0：2.0): 1H-NMR (400 MHz, CDCl3) δ 2.07 (s, 3H), 2.28 (s, 1H), 2.30
(s, 2H), 2.88-2.90 (m, 2H), 3.99-4.03 (m, 1H), 6.17-6.33 (m, 2H), 7.05-7.26 (m, 8H). 13C-NMR (100 MHz,
CDCl3) δ 20.9, 21.0, 30.5, 43.0, 43.4, 49.0, 49.1, 126.0, 127.2, 127.3, 128.2, 128.4, 128.6, 128.9, 129.1,
129.3, 129.6, 130.0, 130.6, 132.1, 132.6, 133.2, 133.9, 135.5, 136.2, 137.1, 139.5, 141.5, 206.3, 206.7. IR
(KBr) 668, 819, 967, 1014, 1091, 1156, 1363, 1404, 1491, 1513, 1539, 1560, 1700, 1715, 1717, 1894,
2919, 3028 cm-1. MS: m/z Calcd. for C19H19ClO: 298.1124; Found: 284.1108, 298.1114.
Mixture of 8f and 8f’ (8f : 8f’ = 1.0：1.5): 1H-NMR (400 MHz, CDCl3) δ 1.11 (d, J = 6.8 Hz, 3H), 1.63 (d,
J = 6.4 Hz, 2H), 2.07 (s, 1H), 2.14 (s, 2H), 2.31 (s, 2H), 2.32 (s, 3H), 2.44 (dd, J = 16.0, 7.6 Hz, 1H), 2.56
(dd, J = 16.0, 6.4 Hz, 1H), 2.75-2.82 (m, 1H), 2.84-2.89 (m, 1H), 3.78-3.81 (m, 0.4H), 5.44-5.54 (m, 1H),
6.07 (dd, J = 16.0, 7.2 Hz, 1H), 6.35 (d, J = 16.0 Hz, 1H), 7.06-7.13 (m, 4H), 7.19-7.26 (m, 2H). 13C-NMR
(100 MHz, CDCl3) δ 8.6, 17.8, 20.2, 21.0, 29.6, 30.5, 30.6, 32.9, 43.5, 46.3, 49.7, 50.7, 125.9, 127.2, 128.4,
129.1, 129.2, 133.4, 133.5, 134.5, 136.8, 140.6, 207.8, 208.2. IR (KBr) 802, 967, 1160, 1359, 1453, 1513,
1716, 1917, 2026, 2924, 2956 cm-1. MS: m/z Calcd. for C14H18O: 202.1358; Found: 202.1357, 202.1359.
1
1
Mixture of 8g and 8g’ (8g : 8g’ = 1.0：4.0): H-NMR (400 MHz, CDCl3) H-NMR (400 MHz, CDCl3) δ
1.11 (d, J = 6.8 Hz, 12H), 1.64 (t, J = 6.0 Hz, 3H), 2.08 (s, 3H), 2.14 (s, 13H), 2.46 (dd, J = 16.0, 6.8 Hz,
4H), 2.56 (dd, J = 16.0, 6.8 Hz, 4H), 2.72-2.80 (m, 2H), 2.82-2.92 (m, 4H), 3.82 (dd, J = 14, 6.8 Hz, 1H),
5.40-5.55 (m, 2H), 6.11 (dd, J = 16.0, 7.2 Hz, 4H), 6.33 (d, J = 16 Hz, 4H), 7.12 (d, J = 8.8 Hz, 2H),
7.25-7.26 (m, 20H). 13C-NMR (100 MHz, CDCl3) δ 17.8, 20.0, 29.6, 30.5, 30.6, 32.7, 43.0, 43.8, 49.3,
50.4, 126.2, 126.6, 127.2, 127.2, 127.4, 127.5, 128.4, 128.5, 128.5, 128.6, 128.8, 129.9, 132.2, 132.5,
132.9, 135.2, 135.8, 137.0, 142.8, 206.8, 207.6. IR (KBr) 699, 746, 807, 967, 1012, 1090, 1159, 1232,
1358, 1406, 1452, 1491, 1699, 1716, 1917, 2021, 2924, 3026, cm-1. MS: m/z Calcd. for C13H15ClO:
222.0811; Found: 222.0820.
References
1. For recent reviews of the α-alkylation of carbonyl compounds, see: (a) J. Mlynarski, B. Gut, B.
Chem. Soc. Rev. 41 (2012) 587-596; (b) P. H.-Y. Cheong, C. Y.;Legault, J. M. Um, N.
Celebi-Olcum, K. N. Houk, Chem. Rev. 111 (2011) 5042-5137; (c) G. Casiraghi, L. Battistini, C.
Curti, G. Rassu, F. Zanardi, Chem. Rev. 111 (2011) 3076-3154; (d) C. Palomo, M. Oiarbide, J. M.

Garcia, J. M. Chem. Soc. Rev. 33 (2004) 65-75; (e) P. Arya, H. Qui, Tetrahedron 56 (2000)
ACCEPTED MANUSCRIPT
917-947; (f) D. Caine, D. In Comprehensive Organic Synthesis, B. M. Trost, I. Fleming, Eds.;
Oxford: New York, 1991 Vol. 9, pp 1-63.; (g) M. T. Reetz, Angew. Chem. Int. Ed. 21 (1982)
96-108.
2. Y. Nishibayashi, I. Wakiji, Y. Ishii, S. Uemura, N. Hidai, M. J. Am. Chem. Soc. 123 (2001)
3393-3394.
3. There are many reports on the direct alkylation of 1,3-dicarbonyl compounds with alcohols. See: (a)
S. A. Babu, M. Yasuda, T. Tsukahara, T. Yamauchi, Y. Wada, A. Baba, A. Synthesis (2008)
1717-1724; (b) Y. Kuninobu, H. Ueda, K. Takai, K. Chem. Lett. 37 (2008) 878-879; (c) P. N. Liu,
Z. Y. Zhou, C. P. Lau, Chem. Eur. J. 13 (2007) 13, 8610-8691; (d) S. Shirakawa, S. Kobayashi,
Org. Lett. 9 (2007) 311-314; (e) R. Sanz, D. Miguel, A. Martinez, J. M. Alvarez-Gutierrez, F.
Rodriguez, Org. Lett. 9 (2007) 2027-2030; (f) P. Angell, P. G. Blazecka, M. Lovdahl, J. Zhang, J.
Org. Chem. 72 (2007) 6006-6015; (g) W. Huang, J. Wang, Q. Shen, X. Zhou, Tetrahedron Lett. 48
(2007) 3969-3973; (h) M. Noji, Y. Konno, K. Ishii, J. Org. Chem. 72 (2007) 5161-5167; (i) J.
Kischel, K. Mertins, D. Michalik, A. Zapf, M. Beller, Adv. Synth. Catal. 349 (2007) 865-870; (j) M.
Rueping, B. J. Nachtsheim, A. Kuenkel, Org. Lett. 9 (2007) 825-828; (k) M. Yasuda, T. Somyo, A.
Baba, Angew. Chem. Int. Ed. 45 (2006) 793-796; (l) H. Kinoshita, H. Shinokubo, K. Oshima, Org.
Lett. 6 (2004) 4085-4088; (m) M. Noji, T. Ohono, K. Fuji, N. Futaba, H. Tajima, K. Ishii, J. Org.
Chem. 68 (2003) 9340-9347; (n) M. Kimura, R. Mukai, N. Tanigawa, S. Tanaka, Y. Tamaru,
Tetrahedron 59 (2003) 7767-7777; (o) K. Manabe, S. Kobayashi, S. Org. Lett. 5 (2003) 3241-3244.
4. Recently, Brønstead acid/trimethyl orthoformate-assisted and Amberlyst-15/ionic liquid-catalyzed
α-alkylation method of ketones with alcohols have been reported. (a) Bronstead acid/trimethyl
orthoformate: S. R. Koppolu, N. Naveen, R. Balamurugan, J. Org. Chem. 79 (2014) 6069-6078. (b)
Amberlyst-15/ionic liquid: K. V. Wagh, B. M. Bhanage, ACS Sustainable Chem. Eng. 4 (2016)
445-450.
5. Direct allylation of ketones with allylic alcohols. See: (a) G. Zhang, J. Wu, H. Zeng, S. Zhang, Z.
Yin, S. Zheng, Org. Lett. 19 (2017) 1080-1083. (b) W. Yao, P. Makowski, C. Giordano, F.
Goettmann, Chem. Eur. J. 15 (2009) 11999-12004. (c) M. Pena-Lopez, P. Piehl, S. Elangovan, H.
Neumann, M. Beller, Angew. Chem. Int. Ed. 55 (2016) 14967-14971.
6. For recent reviews, see: (a) T. D. Nixon, M. K. Whittlesey, J. M. Williams, J. Dalton Trans. (2009)
753-762; (b) F. Shibahara, M. J. Krische, Chem. Lett. 37 (2008) 1102-1107; (c) M. H. S. A.Hamid,
P. A. Slatford, J. M. Williams, J. Adv. Synth. Catal. 349 (2007) 1555-1575; (d) G. Guillena, R. J.
Ramon, M. Yus, Angew. Chem. Int. Ed. 46 (2007) 2358-2364.

7. (a) M. L. Buil, M. A. Esteruelas, J. Herrero, S. Izquierdo, I. M. Pastor, M. Yus, ACS Catal. 3
ACCEPTED MANUSCRIPT
(2013) 2072-2076; (b) M. Dixit, M. Mishra, P. A. Joshi, D. O. Shah, Cat. Commun. 33 (2013)
80-83; (c) S. Liao, K. Yu, Q. Li, H. Tian, Z. Zhang, X. Yu, Q. Xu, Org. Biomol. Chem. 10 (2012)
2973-2978; (d) T. Kuwahara, T. Fukuyama, I. Ryu, Org. Lett. 14 (2012) 4703-4705; (e) X. Cui, Y.
Zhang, F. Shi, Y. Deng, Chem. Eur. J. 17 (2011) 1021-1027; (f) Y. Iuchi, Y. Obora, Y. Ishii, J. Am.
Chem. Soc. 132 (2010) 2536-2537; (g) K. Maeda, Y. Obora, S. Sakaguchi, Y. Ishii, Bull. Chem.
Soc. Jpn. 81 (2008) 689-696; (h) M. Morita, Y. Obora, Y. Ishii, Chem. Commun. (2007)
2850-2852; (i) F. Alonso, P. Riente, M. Yus, Eur. J. Org. Chem. (2008) 4908-4914; (j) Y. M. A.
Yamada, Y. Uozumi, Y. Tetrahedron 63 (2007) 8492-8498; (k) Y. M. A. Yamada, Y. Uozumi, Org.
Lett. 8 (2006) 1375-1378; (l) R. Martinez, D. J. Ramon, M. Yus, Tetrahedron 62 (2006) 8988-9001;
(m) R. Martinez, G. J. Brand, D. J. Ramon, M. Yus, M. Tetrahedron Lett. 46 (2005) 3683-3689; (n)
M. S. Kwon, N. Kim, S. H. Seo, I. S. Park, R. K. Cheedrala, J. J. Park, J. J. Angew. Chem. Int. Ed.
44 (2005) 6913-6915; (o) C. S. Cho, J. Mol. Catal. A: Chem. 240 (2005) 55-60; (p) K. Taguchi, H.
Nakagawa, T. Hirabayashi, S. Sakaguchi, Y. Ishii, J. Am. Chem. Soc. 126 (2004) 72-73; (q) C. S.
Cho, B. T. Kim, T.-J. Kim, S. C. Shim, Tetrahedron Lett. 43 (2002) 7987-7989.
8. M. Morita, S. Sakaguchi, Y. Ishii, J. Org. Chem. 71 (2006) 6285-6286.
9. Y. Nishimoto, Y. Onishi, M. Yasuda, Y. Baba, Angew. Chem. Int. Ed. 48 (2009) 9131-9134.
10. M. Noji, T. Ohno, K. Fuji, N. Futaba, H. Tajima, K. Ishii, J. Org. Chem. 68 (2003) 9340-9347.
11. The use of rhenium complexes in organic synthesis has shown a tremendous potential in the past
few decades. For recent reviews, see: (a) G. Mao, Q. Huang, C. Wang, Eur. J. Org. Chem. (2017)
3549-3564. (b) Y. Kuninobu, Synth. Org. Chem. Jpn. 71 (2013) 425-432; (b) Y. Kuninobu, K.
Takai, Bull. Chem. Soc. Jpn. 85 (2012) 656-671; (c) Y. Kuninobu, K. Takai, Chem. Rev. 111
(2011) 1938-1953; (d) R. Hua, J.-L. Jiang, Curr. Org. Synth. 4 (2007) 151-174; (e) H. Kusama, K.
Narasaka, Synth. Org. Chem. Jpn. 54 (1996) 644-653.
12. For recent examples, see: (a) R. Umeda, M. Kimura, Y. Tobe, Y. Nishiyama, Bull. Chem. Soc. Jpn.
89 (2016) 110-112; (b) R. Umeda, M. Muraki, Y. Nakamura, T. Tanaka, K. Kamiguchi, Y.
Nishiyama, Tetrahedron Lett. 58 (2017) 2393-2395; (c) R. Umeda, H. Tabata, Y. Tobe, Y.
Nishiyama, Chem. Lett. 43 (2014) 883-884; (d) R. Umeda, S. Nishi, A. Kojima, K. Kaiba, Y.
Nishiyama, Tetrahedron Lett. 54 (2013) 179-182; (e) Y. Nishino, T. Tatsuzaki, A. Tsubakihara, Y.
Kuninobu, K. Takai, Synlett (2011) 2585-2589; (f) R. Umeda, K. Kaiba, S. Morishita, Y.
Nishiyama, ChemCatChem 3 (2011) 1743-1746; (g) R. Umeda, T. Nishimura, K. Kaiba, T. Tanaka,
Y. Takahashi, Y. Nishiyama, Tetrahedron 67 (2011) 7217-7221; (h) R. Umeda, K. Kaiba, T.
Tanaka, Y. Takahashi, T. Nishimura, Y.Nishiyama, Y. Synlett (2010) 3089-3091; (i) Y. Nishiyama,
K. Kaiba, R. Umeda, Tetrahedron Lett. 51 (2010) 793-795; (j) Y. Kuninobu, M. Nishi, S. S. Yudha,
K. Takai, K. Org. Lett. 10 (2008) 3009-3011; (k) Y. Nishiyama, K. Shimoura, N. Sonoda,

Tetrahedron Lett. 49 (2008) 6533-6535; (l) Y. Nishiyama, F. Kakushou, N. Sonoda, Tetrahedron
ACCEPTED MANUSCRIPT
Lett. 46 (2005) 787-789; (m) H. Kusama, H. Yamabe, Y. Onizawa, T. Hoshino, N. Iwasawa,
Angew. Chem. Int. Ed. 44 (2005) 468-470; (n) Y. Kuninobu, A. Kawata, K. Takai, K. Org. Lett. 7
(2005) 4823-4825; (o) Y. Nishiyama, F. Kakushou, N. Sonoda, Bull. Chem. Soc. Jpn. 73 (2000)
2779-2782; (p) H. Kusama, K. Narasaka, Bull. Chem. Soc. Jpn. 68 (1995) 2379-2383.
13. R. Umeda, Y. Takahashi, Y. Nishiyama, Tetrahedron Lett. 55 (2014) 6113-6116.
14. Kuninobu and Takai et al. reported the [ReBr(CO)3(thf)]2 complex-catalyzed the coupling reaction
of propynyl alcohols and several nucleophiles, such as 1,3-diketones, β-keto ester, thiols, alcohols
and silyl enol ethers under mild conditions to afford the corresponding coupling products in
moderate to good yields. However, in the case of ReBr(CO)5 as the catalyst, the reaction did not
proceeded. See; Ref. 3b.
15. Although the reaction of 1a and 2a was carried out in the presence of a catalytic amount of AcOH,
the yield of 3a was very low (5 %).
16. It has already reported the rhenium oxide-mediated isomerization of allylic alcohols by the
1,3-transpotion of hydroxyl group. See: Y. Xie, P. F. Floreancig, Angew. Chem. Int. Ed. 52
(2013) 625-628.
17. It has already reported that rhenium complex act as a catalyst on the etherification of alcohols, see:
(a) M. R. Luzung, F. D. Toste, J. Am. Chem. Soc. 125 (2003) 15760-15761; (b) Y. Liu, R. Hua, R.;
H.-B. Sun, X. Qui, X. Organometallics 24 (2005) 2819-2821; (c) Y. Xie, P. E. Floreancig, Angew.
Chem. Int. Ed. 52 (2013) 625-626.
18. (a) F. Zingales, U. Sartorelli, F. Canziani, M. Raveglia, M. Inorg. Chem. 6 (1967) 154-157; (b) P.
W. Jolly, F. G. A. Stone, J. Chem. Soc. (1965) 5259; (c) E. W. Abel, G. B. Hargreaves, G.
Wilkinson, J. Chem. Soc. (1958) 3149.
19. We have shown that C–O bond of ether was effectively cleavage by rhenium complex. See Ref. 13g
and 13h.
20. (a) A. Hajra, N. Yoshikai, E Nakamura, E. Org. Lett. 8 (2006) 4153-4155; (b) Y. Yamamoto, Y. S.
Yamamoto, H. Yatagai, Y. Ishihara, K. Maruyama, K. J. Org. Chem. 47 (1982) 119-126.
21. (a) Y. Onishi, Y. Nishimoto, M. Yasuda, A. Baba, A. Org. Lett. 13 (2011) 2762-2765; (b) K.
Banno, Bull. Chem. Soc. Jpn. 49 (1976) 2284-2291.
22. D. Monguchi, C. Beemelmanns, D. Hashizume, Y. Hamashima, M. Sodeoka, J. Organomet. Chem.
693 (2008) 867-873.
23. (a) C. S. Cho, S. Motofusa, K. Ohe, S. Uemura, S. Bull. Chem. Soc. Jpn. 69 (1996) 2341-2348; (b)
A. Citterio, F. Minisci, E. Vismara, J. Org. Chem. 47 (1982) 81-88.
24. T. Inagaki, L. T. Phong, S. Furuta, J. Ito, H. Nishiyama, H. Chem. Eur. J. 16 (2010) 3090-3096.
25. P. He, Y. Lu, C.-G.Dong, Q.-S. Hu, Org. Lett. 9 (2007) 343-346.

26. B. P. Branchaud, J. Org. Chem. 48 (1983) 3531-3538.
ACCEPTED MANUSCRIPT
27. F. Berttiol, H. Doucet, M. Santelli, Tetrahedron 62 (2006) 4372-4383.
28. J. A. Murphy, A. G. J. Commeureuc, T. N Snaddon,. T. M. McGuire, T. A. Khan, M. L. Dewis, R.
Carling, Org. Lett. 7 (2005) 1427-1429.
29. P. Colbon, J. Ruan, M. Purdie, J.Xian, J. Org. Lett. 12 (2010) 3670-3673
30. L. S.Hegedus, R. E. Williams, M. A. McGuire. T. Hayashi, J. Am. Chem. Soc. 102 (1980)
4973-4979.
31. N. S. C. R. Kumur, V. P. Raj. A. Sudalai, J. Mol. Catal. A.: Chem. 269 (2007) 218-224.
32. E. C. Burger, J. A. Tunge, Org. Lett. 6 (2004) 2603-2605.
33. A. El-Batta, M. Bergdahl, Tetrahedron Lett. 48 (2007) 1761-1765.
34. T. Nishimura, Y. Yasuhara, T. Hayashi, T. Angew. Chem. Int. Ed. 45 (2006) 5164–5166.
35. S. Ogoshi, T. Haba, M. Ohashi, M. J. Am. Chem. Soc. 131 (2009) 10350-10351.
Acknowledgments
This work was financially supported by the MEXT-Supported Program for Grant-in-Aid for Scientific
Research

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Highlights
A new catalytic ability of rhenium complex is described.
A new method of the α-alkylation is developed.
A rhenium-catalyzed carbon-carbon bond formation of the benzylic and allylic alcohols
and enol acetates smoothly proceeded.