Rhodium(I)/cationic 2,2′-bipyridyl-catalyzed [2+2+2] cycloaddition of α,ω-diynes with alkynes in water under air

Article abstract of DOI:10.1016/j.tet.2010.06.088

A simply performed procedure for the [Rh(cod)Cl]₂/cationic 2,2′-bipyridyl system-catalyzed [2+2+2] cycloaddition of α,ω-diynes with terminal and internal alkynes was achieved in water under air at 60 °C. The reaction proceeded smoothly with 1 equiv α,ω-diynes and 3 equiv alkynes in the presence of 20 mol % KOH for 1 h or 9 h, resulting in the formation of tri- and tetra-substituted benzene derivatives in moderate to high yields. After separation of the organic products by extraction, the residual aqueous solution could be reused for further reactions until complete degradation of its catalytic activity.

Full text of DOI:10.1016/j.tet.2010.06.088

Tetrahedron 66 (2010) 7136e7141
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Tetrahedron
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Rhodium(I)/cationic 2,20-bipyridyl-catalyzed [2þ2þ2] cycloaddition of
a,u-diynes
with alkynes in water under air
*
Yun-Hua Wang, Shao-Hsien Huang, Tze-Chiao Lin, Fu-Yu Tsai
Institute of Organic and Polymeric Materials, National Taipei University of Technology, 1, Sec. 3, Chung-Hsiao E. Rd., Taipei 106, Taiwan
a r t i c l e i n f o
a b s t r a c t
A simply performed procedure for the [Rh(cod)Cl]2/cationic 2,20-bipyridyl system-catalyzed [2þ2þ2]
Article history:
Received 20 April 2010
Received in revised form 14 June 2010
Accepted 30 June 2010
Available online 24 July 2010
cycloaddition of a,u
-diynes with terminal and internal alkynes was achieved in water under air at 60 ꢀC.
The reaction proceeded smoothly with 1 equiv a,u-diynes and 3 equiv alkynes in the presence of 20 mol
% KOH for 1 h or 9 h, resulting in the formation of tri- and tetra-substituted benzene derivatives in
moderate to high yields. After separation of the organic products by extraction, the residual aqueous
solution could be reused for further reactions until complete degradation of its catalytic activity.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Reusable catalyst
Water
[2þ2þ2] Cycloaddition
a,u-Diyne
Alkyne
Rhodium
1. Introduction
organic products, enabling the recovered catalyst to be reused in
further reactions.12
Transition-metal-catalyzed [2þ2þ2] cycloaddition of alkynes is
one of the most straightforward methods for the construction of
polysubstituted benzene derivatives.1 Since Reppe and Schweck-
endiek reportedthe first nickel complex-catalyzed cyclotrimerization
of alkynes for the formation of benzene derivatives,2 a large number
of transition-metals including Ru,3 Co,4 Rh,5 Ir,6 Ni,7 Pd,8 and Fe9 have
been employed as catalysts to fulfill this benzene formation reaction.
The reaction is usually carried out in organic solvents under a homo-
geneous phase, and hence it is difficult to separate the precious metal
catalyst from the organic products at the end of the reaction, negating
the possibility of recovery and recycling of the catalyst. Although
there are several examples of the conduction of [2þ2þ2] cycloaddi-
tion reactions in an aqueouseorganic biphasic system,5e alcohol/
water mixed solvents,3e,4a,10 refluxed water,5b and supercritical water
(>374 ꢀC),11 these catalytic reactions were achieved under an inert
atmosphere, and the reusability of such water-soluble catalysts has
not been studied. The developmentof novel water-soluble transition-
metal catalysts to catalyze organic reactions using water as the
reaction medium has been of increasing interest in recent years. The
advantages of such a procedure include not only reasons of safetyand
environmental concern, but also a cost benefit, as aqueous systems
provide opportunity for the separation of the metal catalysts and
We recently developed a water-soluble cationic 2,20-bipyridyl
ligand, 1, to bring transition-metal salts or complexes into the
aqueous phase for employment as a reusable catalytic system to
reduce the wastage of transition-metals. Thus, the SuzukieMiyaura
reaction,13 Hiyama reaction,14 terminal alkynes homocoupling,15
and MizorokieHeck reaction16 can be achieved in water under air
by employing a palladium complex associated with 1 as the cata-
lytic system. In addition, combinations of 1 with FeCl3$6H2O and
[Rh(cod)Cl]2 can be employed as catalysts for S-arylation17 and
phenylacetylenes polymerization18 in an open flask. As part of our
efforts to develop reusable transition-metal-catalyzed organic
Br
NMe
3 Br
Me3N
N
N
1
R
R
[Rh(cod)Cl]2 (3 mol%)/1 (6 mol%)
X
+
X
KOH (20 mol%), H2O, 60oC, in air
R'
R'
2
3 or 5
X = C(CO2Me)2 (2a), C(CH2OMe)2 (2b), NTs (2c), O (2d)
R'
4 or 6
R
= terminal or internal alkyne
* Corresponding author. Fax: þ886 2 2731 7174; e-mail address: fuyutsai@ntut.
Scheme 1. Rhodium(I)-catalyzed [2þ2þ2] cycloaddition in water.
edu.tw (F.-Y. Tsai).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.06.088

Y.-H. Wang et al. / Tetrahedron 66 (2010) 7136e7141
7137
reactions using water as a green solvent, we report herein the ef-
-diynes
and alkynes by [Rh(cod)Cl]2/1 to give polysubstituted benzene
derivatives in water under air. Moreover, the catalyst-containing
aqueous phase can be reused until the complete degradation of its
activity, reducing wastage of the precious metal (Scheme 1).
Although the results indicate that the rhodium catalyst was grad-
ually deactivated during the reaction, it is noteworthy that the re-
sidual aqueous solution could be reused, avoiding wastage of the
precious metal, before its complete deactivation.
Further increasing the amount of 3a did not result in a better
yield of 4a (entry 6). The reaction proceeded slowly in the absence
of KOH, resulting in the formation of 4a in a 67% yield after 24 h
(entry 7). Several studies have shown that abstracting the chloride
of transition-metal complexes by silver salts to produce the cation
ficient catalysis of [2þ2þ2] cycloaddition reactions of
a,u
2. Results and discussion
facilitates [2þ2þ2] cycloaddition of
a,u
-diynes and alkynes.4f,19 In
The [2þ2þ2] cycloaddition represented in Table 1 was con-
ducted in basic water under air at 60 ꢀC using diyne 2a and
1-hexyne 3a as representative reactants. In the absence of ligand 1,
[Rh(cod)Cl]2 was ineffective for the catalysis of the cycloaddition
reaction due to its poor solubility in water, resulting in 88% of 2a
being recovered from the reaction mixture (entry 1). In order to
bring the rhodium catalyst into the aqueous phase, a mixture of
our system, use of the much cheaper KOH was efficient enough to
accelerate the reaction. Reducing the loading amount of catalyst
gave a lower product yield of 4a (entry 8). To demonstrate the
necessity of ligand 1, cycloaddition of 2a and 3a in the presence of
a neutral 2,20-bipydryl ligand gave 4a in only a 9% yield (entry 9).
After the optimal conditions were identified (Table 1, entry 3),
various
a,
u
-diynes and terminal alkynes were used for [2þ2þ2]
Table 1
cycloaddition to explore the scope of the reaction, the results of
which are summarized in Table 2. Compound 2a reacted with
various terminal alkynes effectively in 1 h to give the correspond-
ing products 4be4e in good to high yields (entries 1e4). We pre-
viously discovered that phenylacetylene 3c could be polymerized
very quickly in this catalytic system.17 In this case, addition of the
diyne prior to 3c resulted in the formation of 4c in a 90% yield
(entry 2). It is obvious that the rate of oxidative-coupling of the
diyne to Rh(I) is much faster than the coordination of 3c; hence, the
insertion of 3c into rhodacyclopentadiene, a common intermediate
in the cyclotrimerization and [2þ2þ2] cycloaddition of alkynes, led
to the formation of 4c in high yield. The use of hydrophilic alkyne 3e
resulted in only a 57% yield, presumably owing to its readily
approaching rhodium in the aqueous phase and competing with
the oxidative-coupling of the diyne to the transition-metal
(entry 4). Compound 2b also reacted with terminal alkynes
smoothly to afford indan derivatives in yields between 78% and 82%
(entries 5e7). In addition, [2þ2þ2] cycloaddition of N-tosyl-N,N-
dipropargylamine 2c with terminal alkynes furnished isoindoles
4ie4l at yields between 54% and 76% (entries 8e11). Compound 4k
has been obtained in a 39% yield as one of the products in the
Co2(CO)8-catalyzed tandem [2þ2þ1] and [2þ2þ2] cycloaddition of
2c and 3c at 130 ꢀC under high CO pressure (30 atm).20 In our
system, the same product was synthesized under much milder
reaction conditions in an open flask. Dipropargyl ether 2d is known
for self-cycloaddition;21 thus, increasing the amount of terminal
alkyne and slow addition of 2d into the aqueous solution improved
the yield effectively. The reaction of 2d with 8 equiv of 3a and 3c
under identical conditions gave 4m and 4n in 79% and 72% yields,
respectively (entries 12 and 13). Disappointingly, the cycloaddition
of internal diyne 2e with 3a did not proceed at all, and a near-
quantitative amount of 2e was recovered from the aqueous solution
(entry 14).
Rhodium(I)-catalyzed [2þ2þ2] cycloaddition of diyne (2a) with 1-hexyne (3a)a
Entry
Ligand
Yieldb (%)
1
None
1
1
1
0c
34e
80
53
21
75
67
51
9
2d
3
4f
5g
6h
7i,j
8k
9
1
1
1
1
2,20-Bipyridyl
a
Reaction conditions: 2a (1 mmol), 3a (3 mmol), [Rh(cod)Cl]2 (3 mol %), 1 (6 mol
%), H2O (5 mL), and KOH (20 mol %) at 60 ꢀC in air for 1 h.
b
Isolated yields.
Compound 2a (88%) was recovered.
Compound 3a (1 mmol) was used.
Dimer of 2a (52%) was obtained.
Catalytic aqueous solution reused from entry 3.
Catalytic aqueous solution reused from entry 4.
Compound 3a (5 mmol) was used.
Reaction time of 24 h.
c
d
e
f
g
h
i
j
In the absence of KOH.
[Rh(cod)Cl]2 (2 mol %) and 1 (4 mol %) were used.
k
CH2Cl2 solution (0.5 mL) containing [Rh(cod)Cl]2 (3 mol %) and an
aqueous solution (4 mL) of 1 (6 mol %) was stirred at room tem-
perature for 10 min. After the orange-red aqueous phase had
formed as the upper layer, the solution was heated at 60 ꢀC to
remove CH2Cl2. This in situ-generated catalytic system was then
used for the same reaction under conditions identical to those
described in entry 1, resulting in a 34% yield of 4a along with 52% of
the 2a dimer when equimolar quantities of 2a and 3a were
employed (entry 2). In this system, cyclotrimerization of the
monoalkyne was not observed.
Oshima’s group reported that a hydrophobic diyne such as
diethyl 2,2-diprogargylmalonate could not take part in [2þ2þ2]
annulation due to its insolubility in water.5e Using the system de-
veloped in this study, the quaternary ammonium salts on the 2,20-
bipyridyl ligand may act as a phase transfer agent, bringing the hy-
drophobic reactants, the diyne and monoalkyne, across the interface
into the aqueous phase to facilitate [2þ2þ2] cycloaddition in water.
In order to suppress the self-dimerization or -trimerization of 2a and
improve the yield of the desired product, 3 equiv of 3a was used in
the reaction system. Under the conditions shown in entry 3, 2a had
vanished within 1 h, and after separation of the catalyst from the
organic products by extraction with hexane, the desired product 4a
was isolated in an 80% yield by column chromatography.
We then extended the scope to internal alkynes (Table 3). The
reaction rate for insertion of internal alkynes into rhodacyclo-
pentadiene is much slower than for terminal alkynes owing to the
steric hindrance of the substituents on both sides, and therefore
prolongation of the reaction time to 9 h and the addition of diyne
into the reaction mixture in three portions, one every 3 h, was re-
quired. Under such conditions, 2ae2c reacted with various internal
alkynes giving the corresponding products at yields between 38%
and 77% (entries 1e6), and 2d reacted with 8 equiv of 5d to afford
6g in a 48% yield (entry 7). In contrast with 5d, just 3 equiv of 5b
could react with 2d to deliver 6h in a 52% yield (entry 8).
The possibility that the residual aqueous solution could initiate
the next reaction run if the catalyst was still active was apparent,
and to our delight, we found that two successive reuse runs affor-
ded 4a in 53% and 21% yields, respectively (entries 4 and 5).
3. Conclusion
In conclusion, we successfully employed a [Rh(cod)Cl]2/cat-
ionic 2,20-bipyridyl system to catalyze the [2þ2þ2]

7138
Y.-H. Wang et al. / Tetrahedron 66 (2010) 7136e7141
Table 2
Rhodium(I)/cationic 2,20-bipyridyl-catalyzed [2þ2þ2] cycloaddition of diynes (2) with terminal alkynes (3)a
Entry
Diyne
Terminal alkyne
Product
OMe
Yieldb (%)
78
OMe
C H
6
13
O
O
O
O
1
2a
2a
2a
2a
C6H13
3b
3c
3d
3e
4b
4c
4d
4e
OMe
OMe
OMe
O
2
3
4
90
73
57
O
OMe
O
OMe
CH2OCMe
O
O
O
CH2OCMe
OMe
OMe
CH CH OH
2
2
O
O
CH CH OH
2
2
OMe
C4H9
MeO
MeO
MeO
MeO
5
6
7
2b
2b
2b
C H
3a
3b
3c
4f
81
82
78
4
9
C6H13
MeO
MeO
4g
4h
MeO
MeO
O
S
O
S
C H
4 9
8
N
2c
3a
N
4i
76
O
O
O
S
O
C6H13
9
2c
2c
3b
3c
N
4j
73
68
O
S
O
10
4k
N
N
O
S
O
CH2OH
11
2c
2d
2d
CH2OH
3h
3a
3c
4l
54
79
72
C H
6
13
12c
13c
4m
4n
O
O
O
Me
Me
OMe
OMe
OMe
OMe
Me
Me
C H
O
O
4
9
O
O
14
2e
3a
4o
0d
a
Reaction conditions: 2 (1 mmol), 3 (3 mmol), [Rh(cod)Cl]2 (3 mol %), 1 (6 mol %), H2O (5 mL), and KOH (20 mol %) at 60 ꢀC in air for 1 h.
Isolated yields.
Alkyne (8 mmol) was used.
Compound 2e (95%) was recovered.
b
c
d
cycloaddition of
a
,
u
-diynes and alkynes for the formation of
4. Experimental
4.1. General
benzene derivatives in water under air. This simply performed
procedure in which the reaction was conducted in air using an
environmental-friendly solvent, water, provided the opportunity
for reuse of the catalyst by simple extraction. The employment
of this catalytic system for other organic reactions is now in
progress.
Chemicals were purchased from commercial suppliers and were
used without further purification. Cationic 2,20-bipyridyl ligand 1
was prepared according to the published procedure,13,14 as were

Y.-H. Wang et al. / Tetrahedron 66 (2010) 7136e7141
7139
Table 3
Rhodium(I)/cationic 2,20-bipyridyl-catalyzed [2þ2þ2] cycloaddition of diynes (2) with internal alkynes (5).a
Entry
Diyne
Internal alkyne
Product
Yieldb (%)
OMe
OMe
C H
2
5
O
O
O
O
C H
C H
2 5
1
2a
2a
2a
5a
5b
5c
6a
6b
6c
46
77
40
2
5
C H
2
5
OMe
OMe
O
OMe
CH2OCMe
O
O
O
O
2
3
MeCOH2C
CH2OCMe
CH2OCMe
O
OMe
OMe
OMe
C4H9
O
O
C4H9
C4H9
C4H9
C H
2
MeO
MeO
MeO
MeO
5
5
4
5
2b
2a
5a
5b
6d
6e
38
53
C H
2
O
CH2OCMe
MeO
MeO
CH2OCMe
O
O
O
S
O
O
S
O
CH2OCMe
N
N
6
2c
5b
6f
61
CH2OCMe
O
C H
3
7
7c
2d
2d
C H
3
C H
3 7
5d
5b
6g
6h
48
52
O
O
7
C H
3
7
O
CH2OCMe
8
O
CH2OCMe
O
a
Reaction conditions: 2 (1 mmol), 5 (3 mmol), [Rh(cod)Cl]2 (3 mol %), 1 (6 mol %), H2O (5 mL), and KOH (20 mol %) at 60 ꢀC in air for 9 h.
Isolated yields.
Alkyne (8 mmol) was used.
b
c
diynes 2a,22 2b,6e and 2c,23 and monoalkyne 5b.24 For column
cooling to room temperature, the reaction mixture was extracted
with hexane orEtOAc(5 mL) twice. Thecombined organic phasewas
then dried over MgSO4 and the solvent was removed in a vacuum.
Column chromatography on silica gel afforded the desired product.
chromatography, 70e230-mesh silica gel (Merck Ltd.) was
employed. Melting points were recorded using melting point ap-
paratus and were uncorrected. All 1H and 13C NMR spectra were
recorded in CDCl3 at 25 ꢀC on a Varian 200 NMR spectrometer.
Chemical shifts were reported in parts per million using tetrame-
thylsilane (TMS) as the internal standard. Elemental analyses were
performed and high resolution mass spectra were recorded at the
Instrument Center Service, National Science Council of Taiwan.
4.2.1. 5-Butylindan-2,2-dicarboxylic acid dimethyl ester (4a). Pale
yellow oil.6e EtOAc/hexane¼1/5. 1H NMR (CDCl3, 200 MHz)
d 7.09
(d, J¼7.6 Hz, 1H), 7.01 (s, 1H), 6.98 (d, J¼7.6 Hz,1H), 3.74 (s, 6H), 3.56
(s, 4H), 2.56 (t, J¼7.6 Hz, 2H), 1.34e1.56 (m, 4H), 0.91 (t, J¼7.4 Hz,
3H); 13C NMR (CDCl3, 50 MHz)
d 171.9 (2C), 141.6, 139.7, 136.8, 127.0,
4.2. General procedure for [2D2D2] cycloaddition
124.0, 123.7, 60.3, 52.7 (2C), 40.4, 40.1, 35.3, 33.7, 22.2, 13.8.
To a CH2Cl2 (0.5 mL) solution containing [Rh(COD)Cl]2 (14.7 mg,
0.03 mmol) was added an aqueous solution of 1 (27.6 mg, 0.06 mmol
in 4 mL H2O). The mixture was stirred at room temperature for
10 min, resulting in the formation of an orange-redaqueous phase as
the upper layer. This biphasic solution was then stirred at 60 ꢀC
underan opensystem for 30 min to removeCH2Cl2. Monoalkyne3 or
5 (3 mmol), diyne 2 (1 mmol), and KOH (0.2 mmol in 1 mL H2O)
were added (monoalkyne was added after the addition of the diyne
when phenylacetylene 3c was employed) and the reaction mixture
was stirred at 60 ꢀC for the indicated reaction time (1 h for the re-
actions shown inTables 1 and 2; 9 h for those showninTable 3). After
4.2.2. 5-Hexylindan-2,2-dicarboxylic acid dimethyl ester (4b). Pale
yellow oil.25 EtOAc/hexane¼1/5.1H NMR (CDCl3, 200 MHz)
d 7.09 (d,
J¼7.8 Hz, 1H), 7.00 (s, 1H), 6.99 (d, J¼7.8 Hz, 1H), 3.74 (s, 6H), 3.56 (s,
4H), 2.55 (t, J¼7.2 Hz, 2H), 1.28e1.35 (m, 8H), 0.88 (t, J¼6.4 Hz, 3H);
13C NMR (CDCl3, 50 MHz)
d 171.9 (2C),141.6,139.7,136.8,127.0,124.9,
123.7, 60.3, 52.6 (2C), 40.4, 40.1, 35.7, 31.6, 31.5, 28.9, 22.5, 13.9.
4.2.3. 5-Phenylindan-2,2-dicarboxylic acid dimethyl ester (4c). Light
brown oil.6e EtOAc/hexane¼1/4. 1H NMR (CDCl3, 200 MHz)
d
7.53e7.58 (m, 2H), 7.35e7.46 (m, 4H), 7.30 (d, J¼7.6 Hz, 1H), 7.25
(d, J¼7.6 Hz, 1H), 3.77 (s, 6H), 3.66 (s, 2H), 3.64 (s, 2H); 13C NMR

7140
Y.-H. Wang et al. / Tetrahedron 66 (2010) 7136e7141
(CDCl3, 50 MHz)
127.1 (2C), 126.9, 126.0, 124.4, 122.9, 60.4, 52.9 (2C), 40.5, 40.3.
d
171.9 (2C), 141.1, 140.5, 140.3, 138.9, 128.6 (2C),
140e142 ꢀC). 1H NMR (CDCl3, 200 MHz)
7.31 (d, J¼7.2 Hz, 2H), 7.20 (s, 2H), 7.17 (s, 1H), 4.66 (s, 2H), 4.61 (s,
4H), 2.40 (s, 3H), 1.99 (br, 1H); 13C NMR (CDCl3, 50 MHz)
143.6,
d
7.77 (d, J¼7.2 Hz, 2H),
d
4.2.4. 5-Acetoxymethylindan-2,2-dicarboxylic acid dimethyl ester
141.1, 136.2, 135.0, 133.5, 127.7 (2C), 127.4 (2C), 126.3, 122.4, 120.9,
64.4, 53.5, 53.4, 21.4.
(4d). Pale yellow oil. EtOAc/hexane¼1/2. 1H NMR (CDCl3, 200 MHz)
d
7.20 (s, 1H), 7.17 (s, 2H), 5.10 (s, 2H), 3.75 (s, 6H), 3.59 (s, 4H), 2.09
(s, 3H); 13C NMR (CDCl3, 50 MHz)
d
171.7 (2C), 170.6, 140.2, 139.9,
4.2.13. 5-Hexyl-1,3-dihydro-isobenzofuran (4m). Light brown oil.
134.8, 127.2, 124.1 (2C), 66.1, 60.3, 52.8 (2C), 40.3, 40.2, 20.8. HRMS
calcd for C16H18O6 306.1103; found 306.1109.
EtOAc/hexane¼1/19.1HNMR(CDCl3, 200 MHz)
7.14 (d, J¼7.9 Hz, 1H),
d
7.09 (s, 1H), 7.07 (d, J¼7.9 Hz, 1H), 5.08 (s, 4H), 2.61 (t, J¼7.4 Hz, 2H),
1.31e1.60 (m, 8H), 0.88 (t, J¼6.4 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
4.2.5. 5-(2-Hydroxyethyl)-indan-2,2-dicarboxylic acid dimethyl ester
d 134.6, 130.0,125.5, 125.0, 121.7, 121.6, 69.6, 69.4, 36.0, 31.6, 31.2, 28.8,
(4e). Pale yellow oil.6e EtOAc/hexane¼1/1. 1H NMR (CDCl3,
22.5, 12.0. Anal. Calcd: C, 82.30; H, 9.87. Found: C, 82.52; H, 9.66.
200 MHz)
d
7.22 (d, J¼4.0 Hz, 1H), 7.07 (s, 1H), 7.06 (d, J¼4.0 Hz, 1H),
3.86 (t, J¼6.2 Hz, 2H), 3.75 (s, 6H), 3.58 (s, 4H), 2.83 (t, J¼6.2 Hz, 2H),
4.2.14. 5-Phenyl-1,3-dihydro-isobenzofuran
(4n). Light
brown
1.85 (br, 1H); 13C NMR (CDCl3, 50 MHz)
d
172.0 (2C), 140.2, 137.9,
solid.26 EtOAc/hexane¼1/19. Mp 81e83 ꢀC. 1H NMR (CDCl3,
137.3, 127.7, 124.7, 124.1, 63.6, 60.4, 52.8 (2C), 40.5, 40.2, 40.0.
200 MHz)
50 MHz)
d
7.26e7.61 (m, 8H), 5.17 (s, 4H); 13C NMR (CDCl3,
141.0, 140.8, 140.0, 138.2, 128.8 (2C), 127.3, 127.2 (2C),
d
4.2.6. 5-Butyl-2,2-bismethoxymethylindan (4f). Pale yellow oil.6e
126.5, 121.2, 119.7, 73.5, 73.4.
EtOAc/hexane¼1/14. 1H NMR (CDCl3, 200 MHz)
d 7.06 (d,
J¼7.8 Hz, 1H), 6.98 (s, 1H), 6.94 (d, J¼7.8 Hz, 1H), 3.35e3.36 (m,
10H), 2.79 (s, 4H), 2.56 (t, J¼7.6 Hz, 2H),1.50e1.62 (m, 2H),1.35 (sex,
J¼7.3 Hz, 2H), 0.92 (t, J¼7.3 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
4.2.15. 5,6-Diethylindan-2,2-dicarboxylic acid dimethyl ester (6a).
Pale yellow oil.6e EtOAc/hexane¼1/5. 1H NMR (CDCl3, 200 MHz)
d
6.89 (s, 2H), 3.72 (s, 6H), 3.53 (s, 4H), 2.58 (q, J¼7.6 Hz, 4H), 1.17 (t,
d
142.0, 140.8, 139.1, 126.4, 124.7, 124.4, 76.0 (2C), 59.1 (2C), 48.1,
J¼7.6 Hz, 6H); 13C NMR (CDCl3, 50 MHz)
d 172.1 (2C), 140.5 (2C),
38.8, 38.5, 35.5, 33.9, 22.4, 13.9.
137.3 (2C), 123.8 (2C), 60.5, 52.8 (2C), 40.4 (2C), 25.4 (2C), 15.3 (2C).
4.2.7. 5-Hexyl-2,2-bismethoxymethylindan (4g). Pale yellow oil.
4.2.16. 5,6-Bisacetoxymethylindan-2,2-dicarboxylic acid dimethyl
EtOAc/hexane¼1/14. 1H NMR (CDCl3, 200 MHz)
d
7.06 (d, J¼7.6 Hz,
ester (6b). Light brown oil. EtOAc/hexane¼1/2. 1H NMR (CDCl3,
1H), 6.98 (s,1H), 6.94 (d, J¼7.6 Hz,1H), 3.36 (s, 4H), 3.35 (s, 6H), 2.78
(s, 4H), 2.55 (t, J¼7.4 Hz, 2H), 1.30e1.56 (m, 8H), 0.88 (t, J¼6.2 Hz,
200 MHz) d 7.24 (s, 2H), 5.14 (s, 4H), 3.75 (s, 6H), 3.59 (s, 4H), 2.08 (s,
6H); 13C NMR (CDCl3, 50 MHz)
d 171.7 (2C), 170.5 (2C), 140.6 (2C),
3H); 13C NMR (CDCl3, 50 MHz)
d
142.0, 140.8, 139.1, 126.3, 124.7,
133.4 (2C), 125.8 (2C), 63.7 (2C), 60.3, 53.0 (2C), 40.3 (2C), 20.9 (2C).
Anal. Calcd: C, 60.31; H, 5.86. Found: C, 60.65; H, 5.50.
124.4, 76.4 (2C), 59.0 (2C), 48.1, 38.8, 38.5, 35.8, 31.7 (2C), 29.0, 22.6,
14.0. HRMS calcd for C19H31O2 290.2246; found 290.2250.
4.2.17. 5-Butyl-6-hex-1-ynyl-indan-2,2-dicarboxylic acid dimethyl
4.2.8. 5-Phenyl-2,2-bismethoxymethylindan (4h). Pale yellow oil.
ester (6c). Light brown oil.6e EtOAc/hexane¼1/5. 1H NMR (CDCl3,
EtOAc/hexane¼1/14. 1H NMR (CDCl3, 200 MHz)
d
7.26e7.58 (m,
200 MHz) d 7.19 (s, 1H), 6.99 (s, 1H), 3.74 (s, 6H), 3.54 (s, 2H), 3.52 (s,
8H), 3.40 (s, 4H), 3.37 (s, 6H), 2.88 (s, 2H), 2.87 (s, 2H); 13C NMR
2H), 2.70 (t, J¼7.8 Hz, 2H), 2.42 (t, J¼6.6 Hz, 2H), 1.46e1.62 (m, 6H),
(CDCl3, 50 MHz)
d 142.8, 141.5, 141.3, 139.6, 128.5 (2C), 127.0 (2C),
1.38 (sex., J¼7.8 Hz, 2H), 0.94 (t, J¼7.2 Hz, 3H), 0.93 (t, J¼7.2 Hz, 3H);
126.8, 125.4, 125.0, 123.6, 76.4 (2C), 59.1 (2C), 48.3, 38.9, 38.6. HRMS
calcd for C19H22O2 282.1620; found 282.1629.
13C NMR (CDCl3, 50 MHz)
d 171.8 (2C), 143.6, 139.4, 136.9, 127.5,
124.2, 122.0, 92.9, 79.4, 60.3, 52.8 (2C), 40.4, 40.0, 34.2, 32.9, 30.9,
22.6, 21.9, 19.1, 13.9, 13.5.
4.2.9. 5-Butyl-2-(toluene-4-sulfonyl)-2,3-dihydro-1H-isoindole (4i).
Pale yellow solid. EtOAc/hexane¼1/5. Mp 69e71 ꢀC (lit.3a 70e72 ꢀC).
4.2.18. 5,6-Diethyl-2,2-bismethoxymethylindan (6d). Pale yellow
1
1H NMR (CDCl3, 200 MHz)
d
7.76 (d, J¼8.4 Hz, 2H), 7.30 (d, J¼8.4 Hz,
oil. EtOAc/hexane¼1/14. H NMR (CDCl3, 200 MHz)
d 6.97 (s, 2H),
2H), 7.05 (s, 2H), 6.98 (s, 1H), 4.58 (s, 4H), 2.56 (t, J¼7.2 Hz, 2H), 2.40
(s, 3H), 1.50e1.57 (m, 2H), 1.28e1.37 (m, 2H), 0.90 (t, J¼7.2 Hz, 3H);
3.36 (s, 4H), 3.35 (s, 6H), 2.77 (s, 4H), 2.60 (q, J¼7.6 Hz, 4H), 1.20 (t,
J¼7.6 Hz, 6H); 13C NMR (CDCl3, 50 MHz)
d 139.7 (2C), 139.6 (2C),
13C NMR (CDCl3, 50 MHz)
d
143.3, 142.6, 136.0, 133.7, 133.1, 129.6 (2C),
124.6 (2C), 76.2 (2C), 59.2 (2C), 48.1, 38.8 (2C), 25.5 (2C), 15.5 (2C).
HRMS calcd for C17H26O2 262.1933; found 262.1931.
127.8, 127.4 (2C), 122.3, 122.2, 53.5, 53.4, 35.3, 33.6, 22.1, 21.3, 13.7.
4.2.10. 5-Hexyl-2-(toluene-4-sulfonyl)-2,3-dihydro-1H-isoindole
4.2.19. Acetic acid 6-acetoxymethyl-2,2-bismethoxymethylindan-5-
(4j). Light brown solid. EtOAc/hexane¼1/5. Mp 74e76 ꢀC. 1H NMR
ylmethyl ester (6e). Pale yellow oil. EtOAc/hexane¼1/5. 1H NMR
(CDCl3, 200 MHz)
d
7.76(d, J¼8.1 Hz, 2H),7.30(d,J¼8.1 Hz, 2H),7.05(s,
(CDCl3, 200 MHz) d 7.20 (s, 2H), 5.15 (s, 4H), 3.35 (s, 4H), 3.34 (s, 6H),
2H), 6.97 (s, 1H), 4.58 (s, 4H), 2.55 (t, J¼7.4 Hz, 2H), 2.40 (s, 3H),
2.83 (s, 4H), 2.08 (s, 6H); 13C NMR (CDCl3, 50 MHz)
d 170.5 (2C), 143.1
1.27e1.55 (m, 8H), 0.87 (t, J¼7.0 Hz, 3H); 13C NMR (CDCl3, 50 MHz)
(2C), 132.6 (2C), 126.5 (2C), 76.4 (2C), 64.0 (2C), 59.1 (2C), 48.2, 38.6
(2C), 20.9 (2C). HRMS calcd for C19H26O6 350.1729; found 350.1732.
d
143.0, 142.2, 135.6, 133.3, 132.7, 129.1 (2C), 127.4, 127.0 (2C), 121.8,
121.7, 53.1, 53.0, 35.2, 31.1, 31.0, 28.3, 22.0, 20.9, 13.5. Anal. Calcd: N,
3.92; C, 70.55; S, 8.97; H, 7.61. Found: N, 3.95; C, 70.25; S, 8.69; H, 7.68.
4.2.20. Acetic acid 6-acetoxymethyl-2-(toluene-4-sulfonyl)-2,3-di-
hydro-1H-isoindol-5-ylmethyl ester (6f). Pale yellow solid. EtOAc/
4.2.11. 5-Phenyl-2-(toluene-4-sulfonyl)-2,3-dihydro-1H-isoindole
hexane¼1/1. Mp 148e150 ꢀC. 1H NMR (CDCl3, 200 MHz)
d 7.76 (d,
(4k). Pale yellow solid.20 EtOAc/hexane¼1/5. Mp 175e177 ꢀC. 1H
J¼8.1 Hz, 2H), 7.31 (d, J¼8.1 Hz, 2H), 7.22 (s, 2H), 5.14 (s, 4H), 4.61 (s,
NMR (CDCl3, 200 MHz)
d
7.80 (d, J¼7.4 Hz, 2H), 7.21e7.54 (m, 10H),
4H), 2.41 (s, 3H), 2.07 (s, 6H); 13C NMR (CDCl3, 50 MHz)
d 170.2 (2C),
143.5, 136.5 (2C), 134.2 (2C), 133.4, 129.6 (2C), 127.3 (2C), 123.8 (2C),
63.2 (2C), 53.3 (2C), 21.3, 20.7 (2C). Anal. Calcd: N, 3.36; C, 64.02; S,
7.68; H, 5.55. Found: N, 3.36; C, 64.01; S, 7.72; H, 5.48.
4.67 (s, 4H), 2.41 (s, 3H); 13C NMR (CDCl3, 50 MHz)
d
143.5, 141.0,
140.3, 136.7, 135.0, 133.7, 129.7 (2C), 128.7 (2C), 127.4 (2C), 127.3,
126.9 (2C), 126.7, 122.8, 121.1, 53.6, 53.4, 21.3.
4.2.12. [2-(Toluene-4-sulfonyl)-2,3-dihydro-1H-isoindol-5-yl]metha-
4.2.21. 5,6-Dipropyl-1,3-dihydro-isobenzofuran (6g). Pale yellow oil.
nol (4l). White solid. EtOAc/hexane¼3/2. Mp 139e141 ꢀC (lit.5e
EtOAc/hexane¼1/19. 1H NMR (CDCl3, 200 MHz)
d 7.70 (s, 2H), 5.26

Y.-H. Wang et al. / Tetrahedron 66 (2010) 7136e7141
7141
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(s, 4H), 2.75 (t, J¼7.4 Hz, 4H), 1.65 (sex., J¼7.4 Hz, 4H), 1.00 (t,
J¼7.4 Hz, 6H); 13C NMR (CDCl3, 50 MHz)
d 141.9 (2C), 125.5 (2C),
122.2 (2C), 69.4 (2C), 26.2 (2C), 23.9 (2C), 14.0 (2C). Anal. Calcd: C,
82.30; H, 9.87. Found: C, 82.07; H, 9.98.
ꢀ
ꢀ
ꢀ
4.2.22. Acetic acid 6-acetoxymethyl-1,3-dihydro-isobenzofuran-5-
ylmethyl ester (6h). Pale yellow solid. EtOAc/hexane¼1/3. Mp
76e78 ꢀC. 1H NMR (CDCl3, 200 MHz)
d 7.30 (s, 2H), 5.20 (s, 4H), 5.11
(s, 4H), 2.10 (s, 6H); 13C NMR (CDCl3, 50 MHz)
d 170.4 (2C), 139.8
(2C), 133.3 (2C), 122.4 (2C), 73.2 (2C), 63.6 (2C), 20.8 (2C). HRMS
calcd for C14H16O5 264.0998; found 264.0999.
4.3. Experimental procedure for the reuse of residual
catalytic aqueous solution
This procedure was conducted as described in Section 4.2 under
the reaction conditions shown in entry 3 of Table 1. After cooling
the reaction to room temperature, the aqueous reaction mixture
was washed with hexane under vigorous stirring twice (5 mLꢁ2)
and the organic product isolated from the combined organic phase
according to the previously described procedure. The residual
aqueous solution was then charged with 2a (1 mmol) and 3a
(3 mmol) for the next reaction.
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Acknowledgements
This research was financially supported by the National Science
Council of Taiwan (NSC96-2113-M-027-003-MY2).
Supplementary data
Supplementary data associated with this article can be found in
online version at doi:10.1016/j.tet.2010.06.088.
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