Highly efficient synthesis of functionalized dihydronaphthalenes, tetrahydronaphthalenes, and tetrahydroisoquinolines by iron-catalyzed intramolecular Friedel-Crafts reaction of aryl-containing propargylic alcohols

Article abstract of DOI:10.1016/j.tet.2009.03.007

An efficient, convenient, and one-pot procedure for the synthesis of a series of new dihydro- and tetrahydronaphthalenes as well as tetrahydroisoquinolines has been established through Lewis acid-catalyzed intramolecular Friedel-Crafts reaction of aryl-substituted propargylic alcohols.

Full text of DOI:10.1016/j.tet.2009.03.007

Tetrahedron 65 (2009) 3603–3610
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Highly efficient synthesis of functionalized dihydronaphthalenes,
tetrahydronaphthalenes, and tetrahydroisoquinolines by iron-catalyzed
intramolecular Friedel–Crafts reaction of aryl-containing propargylic alcohols
,b,
Wen Huang a, Longcheng Hong a, Pengzhi Zheng a, Ruiting Liu a, Xigeng Zhou a
*
a Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, People’s Republic of China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient, convenient, and one-pot procedure for the synthesis of a series of new dihydro- and tet-
rahydronaphthalenes as well as tetrahydroisoquinolines has been established through Lewis acid-cata-
lyzed intramolecular Friedel–Crafts reaction of aryl-substituted propargylic alcohols.
Ó 2009 Elsevier Ltd. All rights reserved.
Received 8 January 2009
Received in revised form 2 March 2009
Accepted 3 March 2009
Available online 6 March 2009
Keywords:
Iron
Intramolecular Friedel–Crafts reaction
Tetrahydronaphthalenes
Tetrahydroisoquinolines
1. Introduction
the donating substituent at the benzyl position affects the IFC re-
action. Herein, we wish to report the results. The system allows the
The presence of hydrogenated naphthalene and isoquinoline
ring skeletons in a number of naturally occurring compounds
and synthetic materials, coupled with their role in the fine-
tuning of the biological and/or physical properties of the
compounds for final application, illustrates the need for the
development of new functionalized dihydronaphthalene, tetra-
hydronaphthalene, and tetrahydroisoquinoline-based structures
and new methods for their construction.1,2 The intramolecular
Friedel–Crafts (IFC) reaction3 is an attractive method for the
formation of these types of compounds. However, one of the
challenging problems in such process is the introduction of
appropriate substituents during cyclization because the pres-
ence of functional substituents often prevents the desired IFC
reaction in some cases.4–9
desired IFC reaction of a wide range of applicable substrates under
mild conditions.
2. Results and discussion
We have previously reported that aryl-substituted propargylic
alcohols can serve as new precursors for synthesis of functionalized
spirocyclics, di- and tetrahydronaphthalenes via an intramolecular
Friedel–Crafts reaction.10b However, the method has been limited
to synthesize di- and tetrahydronaphthalenes containing the
electron-withdrawing substituents (ester group) on the non-aro-
matic ring. To understand the influence of the substituents better
and to develop the method further, in this work we firstly made an
extension of this reaction to synthesize di- and tetrahydronaph-
thalenes bearing the electron-donating substituents such as
–CH2OCH3 and –CH2OCH2CH3. The starting materials (1) were
synthesized by the following five-step reactions:11 reaction of
benzyl halides with sodium diethyl malonate in ethanol gave
compounds I, and treatment of I with sodium hydride in THF fol-
lowed by reacting with propargylic bromide led to the formation of
compounds II; reduction of II with LiAlH4 yielded III; the com-
pounds IV were obtained from reaction of III with methyl iodine or
ethyl iodine in the presence of excess KOH; treatment of IV with
In conjunction with our previous research toward the de-
velopment of new methods for the synthesis of biologically active
hydrogenated naphthalenes, spiroindenes, and isoquinolines,10 we
become interested in extending the IFC reaction to other prop-
argylic alcohol substrates, especially, we want to investigate how
* Corresponding author. Tel.: þ86 21 6564 3769; fax: þ86 21 6564 1740.
E-mail address: xgzhou@fudan.edu.cn (X. Zhou).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.03.007

3604
W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
O
O
O
X
NaOEt/EtOH
OEt
OEt
+
R1
EtO
O
OEt
0 °C-r.t., 1-12 h
R1
O
X = Cl or Br
(I)
(1) 1.2 eq. NaH
R1
HO
HO
R1
EtO
(2) propargyl bromide
THF, 0 °C-r.t., 3-12 h
2.2 eq. LiAlH4
EtO
THF, 0 °C-r.t., 3-6 h
(II)
O
(III)
(1) LiHMDS / THF
- 78 °C, 0.5-1 h
(2) R2COR3
- 78 °C-r.t., 3 h
Y
Y
R1
OH
R3
R2
Y
Y
R1
3 eq. MeI or EtI
DMSO, 3 eq. KOH
r.t.-60 °C, 12 h
1
(IV)
1g: R1 = Bu, R2 = R3 = Ph, Y = EtO;
t-
1a: R1 = H, R2 = R3 = Ph, Y = MeO;
1b: R1 = H, R2 = R3 = Ph, Y = EtO;
1c: R1 = Me, R2 = R3 = Ph, Y = EtO;
1d: R1 = MeO, R2 = R3 = Ph, Y = EtO;
1h: R1 = Bu, R2 = R3 = p-ClC6H4, Y = EtO;
t-
1i: R1 = Br, R2 = R3 = Ph, Y = EtO;
1j: R1 = H, R2 = R3 = p-MeC6H4, Y = EtO;
1k: R1 = H, R2 = R3 = p-ClC6H4, Y = EtO;
1l: R1 = H, R2 = Ph, R3 = Me, Y = EtO;
1e: R1 = Me, R2 = R3 = p-ClC6H4, Y = EtO;
1f: R1 = MeO, R2 = R3 = p-ClC6H4, Y = EtO;
Scheme 1. Synthesis of carbon-centered propargylic alcohols 1a–l.
LiHMDS and sequent reaction with ketones gave the propargylic
alcohols 1 (Scheme 1).
including alkyl, alkoxy, and halide. For instance, the introduction
of the electron-donating groups such as methyl and methoxy at
the para-position of the nucleophilic benzene ring had only
a slight influence on the reactivity compared with 1a (Table 1,
entries 3 and 4). Notably, the sterically demanding tert-butyl-
phenyl ring also displayed a high reactivity (Table 1, entries 7
and 8). Even with the presence of an electron-withdrawing
bromide group on the aromatic ring, the cyclization reaction
process was also smooth to give dihydronaphthalene 2i in
moderate yield (Table 1, entry 9).
With the starting materials in hand, we initially studied the
cyclization reaction of propargylic alcohol 1a. Treatment of a nitro-
methane solution of 1a with FeCl3$6H2O (5 mol %) at 80 ꢀC for 15 h
yielded dihydronaphthalene 2a in 62% yield along with some by-
products. Reducing the reaction temperature to 60 ꢀC cleanly gave
2a in 82% isolated yield after 1 h. However, when the reaction
temperature was further lowered to 10–15 ꢀC, tetrahydronaph-
thalene product 3a rather than 2a was selectively obtained in 88%
yield (Scheme 2). In contrast to the reaction of the corresponding
propargylic alcohols containing ester groups that give spirocycle
compounds at 80 ꢀC, attempts to transform 1a or 2a into a spi-
rocyclization product were unsuccessful under the similar condi-
tions. These results indicate that the nature of substituents located
at the dihydronaphthalene ring might play an important role in
controlling the spirocyclization reaction.
Then, the present method was applied to the synthesis of tetra-
hydronaphthalene derivatives under the optimized reaction con-
ditions. Table 2 illustrates the generality of this reaction. Treatment
of a variety of aryl-substituted propargylic alcohols with 5 mol %
FeCl3$6H2O in CH3NO2 at 10–15 ꢀC afforded the corresponding tet-
rahydronaphthalenes products in moderate to good yields, which
depends on the nucleophilicity of the aryl nucleus involved and the
nature of substituents at the propargylic position. It was found that
the substrate containing an electron-withdrawing chloride at the
para-position of the benzene rings located at the propargylic posi-
tion gave the corresponding tetrahydronaphthalene in a higher
yield compared with that bearing an electron-donating methyl in
the same position (Table 2, entries 7 and 8). Furthermore, sub-
stitution of one phenyl at the propargylic position by methyl led to
the decrease of yield (Table 2, entry 9). The results described above
have demonstrated that the nature of substituents at the propargylic
position plays an important role in determining the behavior of
a propargylic cation intermediate. The conjugative effect of aryl
groups is likely to assist the isomerization of propargyl to allenyl. On
the other hand, the strong electron-donating ability of aryl groups
should offer a good stabilizing environment for propargylium and/
or allenylium, and thus may impair the Friedel–Crafts reaction.
Examples of the direct construction of tetrahydroisoquinoline
frameworks by the IFC reaction are very scarce.5b,12 With the aim
of establishing whether the nature of N-substituents would affect
the cyclization reaction of benzylamino-substituted propargylic
alcohols as observed above in synthesis of tetrahydronaph-
thalenes,10a we decided to extend our study on the reaction of
benzylamino-substituted propargylic alcohols that were synthe-
sized by N-sulfonylation of benzylamine followed by N-prop-
argylation, deprotonation, and sequent addition with ketones
(Scheme 3).
Ph
Ph
5 % FeCl3 6H2O
CH3NO2, 60 °C, 1 h
OMe
OMe
2a
82% yield
MeO
MeO
OH
Ph
Ph
Ph
Ph
1a
5 % FeCl3 6H2O
CH3NO2, 15 °C, 0.5 h
OMe
OMe
3a
88% yield
Scheme 2.
With the strategy of controlling selective transformation of
aryl-substituted propargylic alcohols in hand, we firstly explored
the use of the reaction in synthesis of dihydronaphthalene de-
rivatives. A variety of aryl-substituted propargylic alcohol sub-
strates were examined. As shown in Table 1, the results
demonstrated good compatibility with various functional groups,

W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
3605
Table 1
Table 1 (continued)
Synthesis of dihydronaphthalenesa
Entry
Substrate
Product
Yieldb
(%)
Entry
Substrate
Product
Yieldb
(%)
EtO
EtO
t-Bu
OH
MeO
MeO
OH
82
t-Bu
7
81
1
62c
78d
OEt
OEt
OMe
OMe
1g
1a
2g
2a
Cl
EtO
EtO
t-Bu
OH
EtO
EtO
Cl
OH
8e
89
t-Bu
2
81
Cl
OEt
OEt
OEt
OEt
Cl
1h
1b
2b
2h
EtO
EtO
Br
OH
EtO
EtO
Me
OH
9f
66
Br
Me
3
87
OEt
OEt
OEt
OEt
1i
1c
2i
2c
Me
EtO
OH
EtO
EtO
OMe
OH
EtO
Me
MeO
10
72
4
80
Me
OEt
OEt
OEt
OEt
Me
1d
1j
2d
Cl
2j
EtO
EtO
Cl
OH
Cl
EtO
Me
OH
11e
EtO
Cl
Me
85
5e
81
Cl
Cl
Cl
1k
OEt
OEt
OEt
OEt
Cl
EtO
EtO
1e
2e
OH
Me
2k
12g
Cl
EtO
EtO
OMe
OH
1l
Cl
a
General reaction conditions: 0.2–0.3 mmol substrate, 5 mol % of FeCl3$6H2O in
3 mL of CH3NO2 at 60 ꢀC for 1–3 h.
6e
76
MeO
b
Isolated yield.
Cl
c
The reaction was carried out at 80 ꢀC for 15 h.
Using Yb(OTf)3 as a catalyst and the reaction was carried out at 80 ꢀC for 3 h.
1 mL of CH2Cl2 was added to the reaction mixture in order to increase the
OEt
OEt
Cl
1f
d
e
solubility.
2f
f
The reaction time was 24 h.
The reaction gave a complex mixture.
g

3606
W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
Table 2
Table 2 (continued)
Synthesis of tetrahydronaphthalenesa
Entry
Substrate
Product
Yieldb (%)
Entry
Substrate
Product
Yieldb (%)
Cl
Cl
8d
1k
82
88
92c
1
1a
OEt
OEt
OMe
OMe
3k
3a
Me
9
1l
67
OEt
OEt
2
3
4
5
6
1b
1c
1d
1g
1i
90
89
85
83
38
OEt
OEt
3l
a
General reaction conditions: 0.2–0.3 mmol substrate, 5 mol % of FeCl3$6H2O in
3b
3 mL of CH3NO2 at 10–15 ꢀC for 0.2–3 h.
b
Isolated yield.
c
Using Yb(OTf)3 as a catalyst and the product along with about 5% product 2a.
1 mL of CH2Cl2 was added to the reaction mixture in order to increase the
d
solubility.
Me
OEt
OEt
1.3 eq. NEt3
CH2Cl2, 0 °C
NH
R4
R4Cl
R4
+
NH2
3c
(V)
Propargyl bromide,
acetone, K2CO3, 60 °C
N
(1) LiHMDS / THF
- 78 °C, 0.5-1 h
R4
N
MeO
HO
Ph
(2) Ph2CO,
- 78 °C-r.t., 3 h
4
(VI)
Ph
OEt
OEt
Scheme 3. Synthesis of nitrogen-centered propargylic alcohols.
3d
Table
3 summarizes some representative results of the
FeCl3$6H2O (Table 3, Condition A) and Yb(OTf)3 (Table 3, Condition
B) catalyzed reaction of benzylamino-substituted propargylic al-
cohols having various N-substituents. All propargylic substrates (4)
gave the corresponding substituted tetrahydroisoquinolines (5) in
moderate to good yields in the presence of FeCl3$6H2O or Yb(OTf)3
(Table 3, entries 1–5). The reaction was not significantly affected by
the nature of sulfonyl substituents. The methylsulfonyl-substituted
substrate gave the corresponding tetrahydroisoquinoline in
a higher yield compared to the benzylamino-substituted prop-
argylic alcohol containing phenylsulfonyl group (Table 3, entries 1
and 5). Notably, although FeCl3 as a catalyst is cheaper, even more
active than Yb(OTf)3, its reaction conditions such as reaction time
and moisture must be carefully controlled. For the large scales
synthesis of this type of products, Yb(OTf)3 was the better choice as
a catalyst. The structure of 5d was further confirmed by X-ray dif-
fraction analysis, the crystal data clearly demonstrate the isomer-
ization of the propargyl cation to allenyl cation in the
intramolecular Friedel–Crafts reaction process (Fig. 1).13
t-Bu
OEt
OEt
3g
Br
OEt
OEt
3i
Me
Me
3. Conclusion
7
1j
61
In summary, experimentally convenient and cheap catalytic pro-
cesses for regioselective synthesis of a series of new multi-substituted
di- and tetrahydronaphthalenes as well as tetrahydroisoquinoline de-
rivatives from the corresponding aryl-containing propargylic alcohols
via an intramolecular Friedel–Crafts reaction have been established.
Significantsubstrate flexibilityand excellent control of the double bond
OEt
OEt
3j

W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
3607
Table 3
Synthesis of tetrahydroisoquinolinesa
O
S
O
FeCl3 or Yb(OTf)3
CH3NO2
Ph
R
N
OH
Ph
Ph
N
Ph
O
S
4
5
O
R
Entry
Substrate R 4
Product
Con. A,
yieldb (%)
Con. B,
yieldb (%)
Ph
Ph
O
S
N
O
1
C6H5 4a
75
79
5a
Ph
Ph
O
S
N
O
2
p-ClC6H4 4b
80
82
Figure 1. ORTEP diagram of the single-crystal X-ray structure of 5d.
Cl
5b
were recorded at 400 or 500 MHz instrument using tetrame-
thylsilane (TMS) as the internal standard. High resolution mass
spectra (HRMS) were recorded using EI or ESI ionization sources.
Infrared spectra were recorded on a FTIR spectrometer. X-ray
structural analysis was carried out using graphite-monochromated
Ph
Ph
O
S
N
3
p-BrC6H4 4c
77
83
Mo K
a
(
l¼0.71073 Å) radiation. Organic solvents used were dried
by standard methods. Commercially obtained reagents were used
without further purification. All reactions were monitored by TLC
or NMR experiments. Flash column chromatography was carried
out using 300–400 mesh silica gel.
O
Br
5c
Ph
Ph
4.2. Typical procedure for synthesis of dihydronaphthalenes 2
from propargylic alcohols 1
O
N
4c
p-NO2C6H4 4d
86
88
S
To a stirred solution of propargylic alcohol 1a (0.2 mmol) in
nitromethane (3 mL) at 60 ꢀC was added 5 mol % FeCl3$6H2O, and
then the reaction mixture was stirred at this temperature until the
completion of the reaction (monitored by TLC or NMR). The crude
mixture was purified by silica gel column chromatography to pro-
vide the dihydronaphthalene product 2a.
O
NO2
5d
Ph
Ph
5
Me 4e
84
90
4.3. Typical procedure for synthesis of tetrahydro-
naphthalenes 3 from propargylic alcohols 1
O
N
O
S
Me
5e
To a stirred solution of propargylic alcohol 1a (0.2 mmol) in
nitromethane (3 mL) at 15 ꢀC was added 5 mol % FeCl3$6H2O. TLC
analysis showed that the reaction was completed in about 5–
30 min. The crude mixture was directly purified by silica gel col-
umn chromatography to provide the desired product 3a.
a
Condition A: 0.2 mmol substrate, 2 mL of CH3NO2, 20 mol % of FeCl3$6H2O, rt,
0.2–3 h. Condition B: 0.2 mmol substrate, 2 mL of CH3NO2, 5 mol % of Yb(OTf)3,
70 ꢀC, 0.5–3 h.
b
Isolated yield.
c
The structure of product was further confirmed by X-ray diffraction analysis.
and substituent positions render this an attractive method for syn-
thesis of versatile hydrogenated naphthalenes and isoquinolines.
4.4. Characterization data
4.4.1. 4-(2,2-Diphenylvinyl)-2,2-bis(methoxymethyl)-1,2-
dihydronaphthalene (2a)
4. Experimental
4.1. General
Yellow liquid; IR: 3052, 2974, 2932, 2881, 2827, 1596, 1487,
1440, 1196, 1110, 768, 699 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
2.73 (s, 2H), 2.89 (d, J¼9.2 Hz, 2H), 3.02 (d, J¼8.7 Hz, 2H), 3.2
(s, 6H), 5.38 (d, J¼0.9 Hz, 1H), 6.72 (d, J¼0.9 Hz, 1H), 7.13–7.19 (m,
8H), 7.23–7.35 (m, 6H); 13C NMR (CDCl3, 100 MHz):
145.2,
All reactions and manipulations were performed in air unless
otherwise indicated. Melting points are uncorrected. NMR spectra
d

3608
W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
143.0, 140.7, 136.1, 134.5, 134.2, 132.2, 130.1, 128.6, 128.3, 128.1,
128.0, 127.7, 127.6, 127.1, 126.6, 124.3, 74.4, 59.4, 41.1, 32.3; HRMS-
ESI-TOF: calcd for C28H28O2Na ([MþNa]þ): 419.1987, found:
419.1961.
4.4.7. 6-tert-Butyl-4-(2,2-diphenylvinyl)-2,2-bis(ethoxymethyl)-
1,2-dihydronaphthalene (2g)
Colorless viscous liquid; IR: 3048, 2970, 2873, 1596, 1491, 1122,
1095, 695 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
1.27 (s, 9H), 2.68 (s, 2H), 2.95 (d, J¼8.7 Hz, 2H), 3.08 (d, J¼9.2 Hz,
2H), 3.27–3.33 (m, 4H), 5.49 (s, 1H), 6.78 (s, 1H), 7.02 (d, J¼7.8 Hz,
1H), 7.13–7.16 (m, 6H), 7.27–7.38 (m, 6H); 13C NMR (CDCl3,
d
1.07 (t, J¼6.9 Hz, 6H),
4.4.2. 4-(2,2-Diphenylvinyl)-2,2-bis(ethoxymethyl)-1,2-
dihydronaphthalene (2b)
Yellow liquid; IR: 3052, 3017, 2970, 2866, 1596, 1491, 1440,
125 MHz): d 149.0, 144.7, 143.0, 140.7, 135.9, 133.5, 132.8, 131.5,
1110, 1025, 768, 695 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
1.07 (t,
130.0, 128.1, 128.0, 127.9, 127.7, 127.3, 127.0, 126.8, 124.0, 121.0, 71.6,
66.6, 41.0, 34.4, 32.0, 31.4, 15.0; HRMS-EI-TOF: calcd for C34H40O2
(Mþ): 480.3028, found: 480.3028.
J¼6.9 Hz, 6H), 2.73 (s, 2H), 2.92 (d, J¼9.2 Hz, 2H), 3.05 (d,
J¼9.2 Hz, 2H), 3.30–3.33 (m, 4H), 5.42 (s, 1H), 6.73 (d, J¼0.9 Hz,
1H), 7.10–7.15 (m, 5H), 7.17–7.20 (m, 3H), 7.27–7.33 (m, 6H); 13C
NMR (CDCl3, 125 MHz):
d
144.8, 142.8, 140.6, 135.5, 134.6, 134.2,
4.4.8. 4-(2,2-Bis(4-chlorophenyl)vinyl)-6-tert-butyl-2,2-
bis(ethoxymethyl)-1,2-dihydronaphthalene (2h)
132.7, 130.0, 128.4, 128.1, 127.9, 127.8, 127.5, 127.3, 127.0, 126.8,
126.3, 124.0, 71.6, 66.6, 40.9, 32.3, 15.0; HRMS-EI-TOF: calcd for
C30H32O2 (Mþ): 424.2402, found: 424.2401.
Yellow liquid; IR: 3060, 2970, 2866, 1638, 1491, 1382, 1102,
834 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
(s, 9H), 2.68 (s, 2H), 3.00 (d, J¼9.2 Hz, 2H), 3.10 (d, J¼9.2 Hz, 2H),
3.32–3.35 (m, 4H), 5.48 (s, 1H), 6.75 (s, 1H), 7.03–7.08 (m, 3H),
7.15–7.18 (m, 3H), 7.22–7.30 (m, 5H); 13C NMR (CDCl3, 125 MHz):
d
1.09 (t, J¼7.3 Hz, 6H), 1.27
4.4.3. 4-(2,2-Diphenylvinyl)-2,2-bis(ethoxymethyl)-6-methyl-1,2-
dihydronaphthalene (2c)
White solid; mp: 87–88 ꢀC; IR: 3009, 2974, 2862, 1631, 1495,
d 149.1, 142.1, 141.0, 138.7, 135.5, 133.6, 133.3, 133.1, 133.0, 131.5,
1444, 1386, 1118, 765, 695 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
1.06
131.3, 129.3, 128.5, 128.2, 128.1, 124.3, 120.8, 71.7, 66.6, 41.0, 34.4,
32.1, 31.4, 15.0; HRMS-EI-TOF: calcd for C34H38Cl2O2 (Mþ):
548.2249, found: 548.2252.
(t, J¼6.9 Hz, 6H), 2.28 (s, 3H), 2.68 (s, 2H), 2.91 (d, J¼9.2 Hz, 2H),
3.05 (d, J¼9.2 Hz, 2H), 3.19–3.32 (m, 4H), 5.42 (s, 1H), 6.73 (d,
J¼0.9 Hz, 1H), 6.94–7.01 (m, 2H), 7.12–7.20 (m, 6H), 7.26–7.37 (m,
5H); 13C NMR (CDCl3, 125 MHz):
d
144.6, 142.9, 140.6, 135.6, 135.5,
4.4.9. 6-Bromo-4-(2,2-diphenylvinyl)-2,2-bis(ethoxymethyl)-1,2-
dihydronaphthalene (2i)
134.0, 132.8,131.5,130.0,128.3,128.1,127.9,127.8,127.4,127.2,126.8,
124.8, 71.6, 66.5, 40.9, 31.8, 21.1, 15.0; HRMS-EI-TOF: calcd for
C31H34O2 (Mþ): 438.2559, found: 438.2560.
Yellow viscous liquid; IR: 3075, 2970, 2862,1642,1386,1118, 761,
691 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
1.07 (t, J¼7.3 Hz, 6H), 2.66
(s, 2H), 2.91 (d, J¼9.2 Hz, 2H), 3.01 (d, J¼9.2 Hz, 2H), 3.30 (q,
J¼7.3 Hz, 4H), 5.50 (s, 1H), 6.66 (d, J¼0.9 Hz, 1H), 6.97 (d, J¼7.8 Hz,
1H), 7.11–7.13 (m, 2H), 7.18–7.25 (m, 4H), 7.28–7.35 (m, 5H), 7.41 (d,
4.4.4. 4-(2,2-Diphenylvinyl)-2,2-bis(ethoxymethyl)-6-methoxy-1,2-
dihydronaphthalene (2d)
Yellow viscous liquid; IR: 3017, 2866, 1603, 1483, 1382, 1114,
J¼1.8 Hz, 1H); 13C NMR (CDCl3, 125 MHz):
d 145.5, 142.5, 140.3,
765, 695 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
1.07 (t, J¼6.9 Hz,
136.2, 134.7, 134.3, 133.5, 129.8, 128.0, 127.8, 127.6, 127.0, 126.9,
125.9, 120.0, 71.4, 66.6, 40.9, 31.7, 15.0; HRMS-EI-TOF: calcd for
C30H31BrO2 (Mþ): 502.1507, found: 052.1508.
6H), 2.65 (s, 2H), 2.91 (d, J¼9.2 Hz, 2H), 3.05 (d, J¼9.2 Hz, 2H),
3.30–3.33 (m, 4H), 3.75 (s, 3H), 5.46 (s, 1H), 6.67–6.71 (m, 2H),
6.90 (d, J¼2.7 Hz, 1H), 7.02 (d, J¼8.2 Hz, 1H), 7.12–7.28 (m, 5H),
7.27–7.35 (m, 5H); 13C NMR (CDCl3, 125 MHz):
d
158.3, 144.9,
4.4.10. 4-(2,2-Di-p-tolylvinyl)-2,2-bis(ethoxymethyl)-1,2-
142.8, 140.5, 135.5, 135.2, 133.5, 130.0, 129.0, 128.1, 127.9, 127.8,
127.4, 126.9, 126.8, 126.6, 111.8, 110.5, 71.5, 66.6, 55.3, 41.2, 31.4,
15.0; HRMS-EI-TOF: calcd for C31H34O3 (Mþ): 454.2508, found:
454.2507.
dihydronaphthalene (2j)
Yellow liquid; IR: 3017, 2970, 2866, 1603, 1506, 1110, 815 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
2.34 (s, 3H), 2.73 (s, 2H), 2.93 (d, J¼9.2 Hz, 2H), 3.06 (d, J¼9.2 Hz,
2H), 3.29–3.32 (m, 4H), 5.41 (s, 1H), 6.66 (s, 1H), 6.98–7.03 (m,
4H), 7.09–7.14 (m, 5H), 7.23–7.32 (m, 3H); 13C NMR (CDCl3,
d
1.07 (t, J¼6.9 Hz, 6H), 2.29 (s, 3H),
4.4.5. 4-(2,2-Bis(4-chlorophenyl)vinyl)-2,2-bis(ethoxymethyl)-6-
methyl-1,2-dihydronaphthalene (2e)
125 MHz):
d 144.6, 140.2, 137.7, 137.2, 136.2, 135.6, 134.6, 134.3,
Yellow viscous liquid; IR: 3048, 2970, 2850, 1634, 1487, 1378,
132.4, 129.8, 128.8, 128.4, 128.3, 127.8, 127.2, 126.2, 125.9, 124.0,
71.7, 66.5, 40.9, 32.3, 21.1, 21.0, 15.0; HRMS-EI-TOF: calcd for
C32H36O2 (Mþ): 452.2715, found: 452.2715.
1106, 1013, 831 cmꢁ1
; d 1.08 (t,
1H NMR (CDCl3, 400 MHz):
J¼7.3 Hz, 6H), 2.28 (s, 3H), 2.68 (s, 2H), 2.96 (d, J¼9.2 Hz, 2H), 3.08
(d, J¼9.2 Hz, 2H), 3.32 (q, J¼7.3 Hz, 4H), 5.42 (s, 1H), 6.72 (s, 1H),
6.96–7.07 (m, 5H), 7.17–7.19 (m, 2H), 7.23–7.31 (m, 4H); 13C NMR
4.4.11. 4-(2,2-Bis(4-chlorophenyl)vinyl)-2,2-bis(ethoxymethyl)-1,2-
dihydronaphthalene (2k)
(CDCl3, 125 MHz):
d 142.3, 141.0, 138.6, 135.7, 135.2, 133.6, 133.4,
133.0, 131.5, 131.3, 129.6, 129.1, 128.6, 128.4, 128.2, 128.1, 124.6,
71.6, 66.6, 41.0, 32.0, 21.2, 15.0; HRMS-EI-TOF: calcd for
C31H32Cl2O2 (Mþ): 506.1779, found: 506.1782.
Yellow liquid; IR: 2970, 2862, 1631, 1483, 1382, 1091, 831,
776 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
1.08 (t, J¼6.9 Hz, 6H), 2.73 (s,
2H), 2.97 (d, J¼8.7 Hz, 2H), 3.08 (d, J¼9.2 Hz, 2H), 3.32 (q, J¼6.9 Hz,
4H), 5.43 (s,1H), 6.72 (s,1H), 7.05 (d, J¼8.2 Hz, 2H), 7.10–7.19 (m, 5H),
4.4.6. 4-(2,2-Bis(4-chlorophenyl)vinyl)-2,2-bis(ethoxymethyl)-6-
methoxy-1,2-dihydronaphthalene (2f)
7.21–7.28 (m, 5H); 13C NMR (CDCl3, 125 MHz):
d 142.3, 140.8, 138.6,
135.1, 134.6, 133.8, 133.6, 133.2, 133.0, 131.3, 129.1, 128.5, 128.4, 128.2,
128.0, 127.5, 126.3, 123.8, 71.6, 66.6, 41.0, 32.4, 15.0; HRMS-EI-TOF:
calcd for C30H30Cl2O2 (Mþ): 492.1623, found: 492.1627.
White solid; mp: 108–109 ꢀC; IR: 3021, 2974, 2866, 1572,
1483, 1099, 831 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.08 (t,
J¼7.3 Hz, 6H), 2.66 (s, 2H), 2.96 (d, J¼9.2 Hz, 2H), 3.08 (d,
J¼9.2 Hz, 2H), 3.32 (q, J¼7.3 Hz, 4H), 3.76 (s, 3H), 5.46 (s, 1H),
6.69 (s, 1H), 6.71 (d, J¼2.3 Hz, 1H), 6.83 (d, J¼2.3 Hz, 1H),
7.03–7.07 (m, 3H), 7.17–7.29 (m, 6H); 13C NMR (CDCl3,
4.4.12. 1-(2,2-Diphenylvinylidene)-3,3-bis(methoxymethyl)-1,2,3,4-
tetrahydronaphthalene (3a)
White solid; mp: 128–129 ꢀC; IR: 2986, 2928, 2885, 2811, 1926,
125 MHz):
d
158.3, 142.7, 140.8, 138.5, 135.1, 134.8, 134.0,
1596, 1448, 1382, 1114, 768, 695 cmꢁ1 1H NMR (CDCl3, 400 MHz):
;
133.6, 133.0, 131.3, 129.2, 129.1, 128.4, 128.2, 127.8, 126.6,
111.8, 110.6, 71.6, 66.6, 55.3, 41.2, 31.5, 15.0; HRMS-EI-TOF:
calcd for C31H32Cl2O3 (Mþ): 522.1729, found: 522.1729.
d
2.68 (s, 2H), 2.78 (s, 2H), 3.28–3.36 (m, 10H), 7.10–7.11 (m, 3H),
7.22–7.32 (m, 6H), 7.39–7.42 (m, 4H), 7.56–7.58 (m, 1H); 13C NMR
(CDCl3, 100 MHz): 206.7, 137.2, 134.6, 130.7, 130.2, 128.6, 128.5,
d

W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
3609
127.5, 127.4, 126.6, 126.3, 112.8, 102.9, 75.7, 59.5, 38.8, 34.9, 32.9;
HRMS-ESI-TOF: calcd for C28H28O2Na ([MþNa]þ): 419.1987, found:
419.1991.
129.0, 128.3, 127.1, 126.4, 126.0, 112.2, 102.6, 73.3, 66.8, 38.7, 34.6,
32.7, 21.1, 15.1; HRMS-EI-TOF: calcd for C32H36O2 (Mþ): 452.2715,
found: 452.2716.
4.4.19. 1-(2,2-Bis(4-chlorophenyl)vinylidene)-3,3-bis(ethoxy-
methyl)-1,2,3,4-tetrahydronaphthalene (3k)
4.4.13. 1-(2,2-Diphenylvinylidene)-3,3-bis(ethoxymethyl)-1,2,3,4-
tetrahydronaphthalene (3b)
White solid; mp: 145–146 ꢀC; IR: 3048, 2974, 2866, 1926, 1483,
White solid; mp: 85–87 ꢀC; IR: 3017, 2974, 2862,1926,1487,1382,
1390, 1106, 831, 761 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.12 (t,
1102, 776, 695 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
1.12 (t, J¼7.3 Hz,
J¼7.3 Hz, 6H), 2.69 (s, 2H), 2.80 (s, 2H), 3.33–3.44 (m, 8H), 7.10–7.14
6H), 2.70 (s, 2H), 2.80 (s, 2H), 3.34–3.44 (m, 8H), 7.09–7.11 (m, 3H),
(m, 3H), 7.26–7.32 (m, 8H), 7.48 (d, J¼7.2 Hz, 1H); 13C NMR (CDCl3,
7.19–7.32 (m, 6H), 7.40–7.43 (m, 4H), 7.55–7.58 (m, 1H); 13C NMR
125 MHz):
d 206.5, 135.3, 135.0, 133.2, 130.1, 130.0, 129.6, 128.6,
(CDCl3, 125 MHz):
d 206.6, 137.1, 134.8, 130.6, 130.0, 128.4, 128.3,
127.6, 126.3, 126.1, 110.8, 103.9, 73.2, 66.8, 38.7, 34.6, 32.5, 15.1;
HRMS-EI-TOF: calcd for C30H30Cl2O2 (Mþ): 492.1623, found:
492.1625.
127.3,127.2,126.4,126.0,112.6,103.0, 73.3, 66.8, 38.7, 34.7, 32.7,15.0;
HRMS-EI-TOF: calcd for C30H32O2 (Mþ): 424.2402, found: 424.2400.
4.4.14. 1-(2,2-Diphenylvinylidene)-3,3-bis(ethoxymethyl)-7-
methyl-1,2,3,4-tetrahydronaphthalene (3c)
4.4.20. 3,3-Bis(ethoxymethyl)-1-(2-phenylprop-1-enylidene)-
1,2,3,4-tetrahydronaphthalene (3l)
Yellow sticky liquid; IR: 3056, 2970, 2866, 1926, 1596, 1483,
1382, 1130, 765, 691 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.12 (t,
Yellow liquid; IR: 3060, 2966, 2866, 1930, 1596, 1487, 1106,
757 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.12–1.21 (m, 6H), 2.19 (s,
J¼6.9 Hz, 6H), 2.26 (s, 3H), 2.68 (s, 2H), 2.76 (s, 2H), 3.33–3.43 (m,
3H), 2.56 (d, J¼14.2 Hz, 1H), 2.61 (d, J¼14.2 Hz, 1H), 2.79 (s, 2H),
8H), 6.94 (d, J¼7.8 Hz, 1H), 7.01 (d, J¼7.8 Hz, 1H), 7.21–7.36 (m, 7H),
7.41–7.43 (m, 4H); 13C NMR (CDCl3, 125 MHz):
d 206.6, 137.2, 135.5,
3.36–3.48 (m, 8H), 7.05–7.21 (m, 4H), 7.25–7.31 (m, 2H), 7.39–7.43
(m, 3H); 13C NMR (CDCl3, 125 MHz):
d 204.5, 137.4, 134.6, 131.2,
131.8, 130.2, 129.8, 128.5, 128.4, 128.3, 127.2, 126.7, 112.4, 103.1, 73.3,
66.7, 38.8, 34.3, 32.8, 21.1, 15.1; HRMS-EI-TOF: calcd for C31H34O2
(Mþ): 438.2559, found: 438.2559.
129.9, 128.3, 126.9, 126.6, 126.5, 125.9, 125.8, 103.2, 101.7, 73.5, 66.8,
38.6, 34.5, 32.8, 16.9, 15.1, 15.0; HRMS-EI-TOF: calcd for C25H30O2
(Mþ): 362.2246, found: 362.2245.
4.4.15. 1-(2,2-Diphenylvinylidene)-3,3-bis(ethoxymethyl)-7-
methoxy-1,2,3,4-tetrahydronaphthalene (3d)
4.4.21. 4-(2,2-Diphenylvinylidene)-2-(phenylsulfonyl)-1,2,3,4-
tetrahydroisoquinoline (5a)
Yellow viscous liquid; IR: 3001, 2970, 2873, 1930, 1603, 1491,
1386, 1269, 1091, 695 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.12 (t,
Brown liquid; IR: 3052, 3013, 1930, 1487, 1440, 1168, 1087, 726,
695 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
4.36 (s, 2H), 4.47 (s, 2H),
7.02–7.09 (m, 3H), 7.17–7.21 (m, 2H), 7.27–7.36 (m, 12H), 7.67–7.70
(m, 2H); 13C NMR (CDCl3, 100 MHz):
203.5, 137.3, 136.1, 132.9,
J¼6.9 Hz, 6H), 2.68 (s, 2H), 2.73 (s, 2H), 3.32–3.43 (m, 8H), 3.71
(s, 3H), 6.71–6.74 (m, 1H), 7.03 (d, J¼8.7 Hz, 1H), 7.10–7.11 (m,
1H), 7.24–7.33 (m, 6H), 7.40–7.43 (m, 4H); 13C NMR (CDCl3,
d
130.8, 129.0, 128.8, 128.7, 128.6, 128.1, 127.9, 127.8, 127.6, 126.8,
126.6, 116.0, 99.9, 48.6, 47.3; HRMS-ESI-TOF: calcd for C29H24NO2S
([MþH]þ): 450.1528, found: 450.1537.
125 MHz):
d 206.5, 157.7, 137.1, 131.5, 130.8, 128.4, 128.3, 127.2,
127.1, 113.9, 112.7, 110.5, 103.1, 73.2, 66.7, 55.1, 38.8, 33.9, 32.6,
15.1; HRMS-EI-TOF: calcd for C31H34O3 (Mþ): 454.2508, found:
454.2505.
4.4.22. 2-(4-Chlorophenylsulfonyl)-4-(2,2-diphenylvinylidene)-
1,2,3,4-tetrahydroisoquinoline (5b)
4.4.16. 7-tert-Butyl-1-(2,2-diphenylvinylidene)-3,3-bis(ethoxy-
methyl)-1,2,3,4-tetrahydronaphthalene (3g)
Brown viscous liquid; IR: 3013, 2924, 1938, 1448, 1382, 1343,
1165,1091, 815 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
4.45 (s, 2H), 4.56
(s, 2H), 7.02–7.15 (m, 5H), 7.30–7.37 (m, 11H), 7.52–7.55 (m, 2H); 13C
NMR (CDCl3, 100 MHz): 203.1, 139.1, 136.3, 136.0, 130.4, 129.1,
Yellow liquid; IR: 3013, 2974, 2869, 1933, 1491, 1110, 912,
695 cmꢁ1
;
1H NMR (CDCl3, 400 MHz):
d
1.13 (t, J¼6.9 Hz, 6H), 1.26
d
(s, 9H), 2.68 (s, 2H), 2.76 (s, 2H), 3.34–3.45 (m, 8H), 7.05 (d, J¼7.8 Hz,
1H), 7.16–7.33 (m, 7H), 7.41–7.43 (m, 4H), 7.60 (d, J¼1.8 Hz, 1H); 13C
129.0, 128.7, 128.6, 128.5, 128.1, 127.8, 127.6, 126.7, 126.6, 115.8, 99.3,
48.7, 47.2; HRMS-ESI-TOF: calcd for C29H22ClNO2SNa ([MþNa]þ):
506.0957, found: 506.0981.
NMR (CDCl3, 125 MHz):
d 206.4, 148.7, 137.4, 131.8, 129.9, 129.6,
128.4, 128.3, 127.1, 124.7, 123.0, 112.5, 103.3, 73.3, 66.7, 38.8, 34.3,
34.2, 32.7, 31.3, 15.1; HRMS-EI-TOF: calcd for C34H40O2 (Mþ):
480.3028, found: 480.3028.
4.4.23. 2-(4-Bromophenylsulfonyl)-4-(2,2-diphenylvinylidene)-
1,2,3,4-tetrahydroisoquinoline (5c)
Brown solid; mp: 149–151 ꢀC; IR: 3023, 1933, 1568, 1436, 1347,
4.4.17. 7-Bromo-1-(2,2-diphenylvinylidene)-3,3-bis(ethoxy-
methyl)-1,2,3,4-tetrahydronaphthalene (3i)
1157, 932 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d 4.44 (s, 2H), 4.54 (s, 2H),
7.03–7.22 (m, 5H), 7.28–7.39 (m,11H), 7.45 (d, J¼8.2 Hz, 2H); 13C NMR
Yellow viscous liquid; IR: 2974, 1926, 1491, 1386, 1099, 772,
692 cmꢁ1; 1H NMR (CDCl3, 400 MHz):
d
1.12 (t, J¼6.9 Hz, 6H), 2.68
(CDCl3,100 MHz):d203.1,136.8,136.0,132.0,130.4,129.2,128.8,128.6,
128.5,128.1,127.9,127.7,126.8,126.6,115.8,99.3, 48.7, 47.2;HRMS-ESI-
(s, 2H), 2.73 (s, 2H), 3.31–3.42 (m, 8H), 6.97 (d, J¼7.8 Hz, 1H),
TOF: calcd for C29H23BrNO2S ([MþH]þ): 528.0633, found: 528.0643.
7.21–7.24 (m, 1H), 7.25–7.43 (m, 10H), 7.65 (s, 1H); 13C NMR
(CDCl3, 125 MHz):
d 206.3, 136.6, 133.6, 132.9, 131.5, 130.2, 128.9,
4.4.24. 4-(2,2-Diphenylvinylidene)-2-(4-nitrophenylsulfonyl)-
1,2,3,4-tetrahydroisoquinoline (5d)
128.4, 128.3, 127.4, 119.7, 113.1, 102.2, 73.1, 66.7, 38.5, 34.1, 32.5,
15.0; HRMS-EI-TOF: calcd for C30H31BrO2 (Mþ): 502.1507, found:
502.1508.
Yellow solid; mp: 181–183 ꢀC; IR: 3027, 1928, 1527, 1446, 1347,
1311, 1168, 1091 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 4.57 (s, 2H),
4.67 (s, 2H), 7.01–7.05 (m, 2H), 7.09–7.11 (m, 1H), 7.20–7.22 (m, 1H),
4.4.18. 1-(2,2-Di-p-tolylvinylidene)-3,3-bis(ethoxymethyl)-1,2,3,4-
tetrahydronaphthalene (3j)
7.27–7.30 (m, 4H), 7.35–7.40 (m, 6H), 7.65–7.71 (m, 4H); 13C NMR
White solid; mp: 109–111 ꢀC, IR: 3021, 2920, 2850, 1926, 1506,
(CDCl3, 100 MHz):
d 202.7, 149.7, 144.2, 135.8, 130.0, 128.9, 128.8,
1479, 1110, 823, 761 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 1.12 (t,
128.6, 128.4, 128.0, 127.9, 126.8, 126.5, 123.6, 116.2, 98.6, 48.9, 47.4.
Anal. Calcd for C29H22N2O4S: C, 70.43; H, 4.48; N, 5.66. Found: C,
70.35; H, 4.52; N, 5.64. HRMS-ESI-TOF: calcd for C29H22N2O4SNa
([MþNa]þ): 517.1198, found: 517.1216.
J¼7.3 Hz, 6H), 2.34 (s, 6H), 2.68 (s, 2H), 2.79 (s, 2H), 3.32–3.44 (m,
8H), 7.06–7.12 (m, 7H), 7.27–7.32 (m, 4H), 7.53–7.58 (m, 1H); 13C
NMR (CDCl3, 125 MHz):
d 206.2, 136.9, 134.7, 134.3, 130.8, 129.9,

3610
W. Huang et al. / Tetrahedron 65 (2009) 3603–3610
5. (a) Ma, S.; Zhang, J. Tetrahedron Lett. 2002, 43, 3435; (b) Ma, S.; Zhang, J.
Tetrahedron 2003, 49, 6273.
6. Kurteva, V. B.; Santos, A. G.; Afonso, C. A. M. Org. Biomol. Chem. 2004, 2, 514.
7. Hayashi, R.; Cook, G. R. Org. Lett. 2007, 9, 1311.
8. Selected other approaches: (a) Bandini, M.; Eichholzer, A.; Kotrusz, P.; Umani-
Ronchi, A. Adv. Synth. Catal. 2008, 350, 531; (b) Grise´, C. M.; Barriault, L. Org.
4.4.25. 4-(2,2-Diphenylvinylidene)-2-(methylsulfonyl)-1,2,3,4-
tetrahydroisoquinoline (5e)
Brown solid; mp: 191–193 ꢀC; IR: 3017, 2823, 1930, 1487, 1351,
1157, 947, 780, 695 cmꢁ1 1H NMR (CDCl3, 400 MHz):
; d 2.63 (s,
3H), 4.55 (s, 2H), 4.68 (s, 2H), 7.14–7.17 (m, 1H), 7.23–7.25 (m,
´
Lett. 2006, 8, 5905; (c) Grise, C. M.; Rodrigue, E. M.; Barriault, L. Tetrahedron
2H), 7.28–7.40 (m, 10H), 7.61–7.63 (m, 1H); 13C NMR (CDCl3,
2008, 64, 797; (d) Lin, M. Y.; Das, A.; Liu, R. S. J. Am. Chem. Soc. 2006, 128, 9340;
(e) Mamane, V.; Hannen, P.; Fu¨ rstner, A. Chem.dEur. J. 2004, 10, 4556; (f)
Lautens, M.; Rovis, T. J. Org. Chem. 1997, 62, 5246; (g) Hilt, G.; Lu¨ ers, S.; Smolko,
K. I. Org. Lett. 2005, 7, 251; (h) Namba, K.; Yamamoto, H.; Sasaki, I.; Mori, K.;
Imagawa, H.; Nishizawa, M. Org. Lett. 2008, 10, 1767; (i) Bandini, M.; Eichholzer,
A.; Kotrusz, P.; Tragni, M.; Troisi, S.; Umani-Ronchi, A. Adv. Synth. Catal. 2009,
351, 319.
9. The intramolecular Friedel–Crafts reaction to synthesis quinoline and iso-
chromane derivatives from propargylic derivatives, see: (a) Ishikawa, T.; Okano,
M.; Aikawa, T.; Saito, S. J. Org. Chem. 2001, 66, 4635; (b) Ishikawa, T.; Manabe, S.;
Aikawa, T.; Kudo, T.; Saito, S. Org. Lett. 2004, 6, 2361.
10. (a) Huang, W.; Shen, Q. S.; Wang, J. L.; Zhou, X. G. J. Org. Chem. 2008, 73, 1586;
(b) Huang, W.; Zheng, P. Z.; Zhang, Z. X.; Liu, R. T.; Chen, Z. X.; Zhou, X. G. J. Org.
Chem. 2008, 73, 6845.
11. (a) Wu, Z. X.; Minhas, G. S.; Wen, D.; Jiang, H. L.; Chen, K. X.; Zimniak, P.;
Zheng, J. J. Med. Chem. 2004, 47, 3282; (b) Cadran, N.; Cariou, K.; Herve´, G.;
Aubert, C.; Fensterbank, L.; Malacria, M.; Marco-Contelles, J. J. Am. Chem.
Soc. 2004, 126, 3408; (c) Chatani, N.; Inoue, H.; Ikeda, T.; Murai, S. J. Org.
Chem. 2000, 65, 4913; (d) Trost, B. M.; Rudd, M. T. J. Am. Chem. Soc. 2005,
127, 4763.
12. Selected examples by Lewis acid catalyzed intramolecular cyclization reaction:
(a) Roesch, K. R.; Larock, R. C. J. Org. Chem. 2002, 67, 86; (b) Dai, G.; Larock, R. C.
J. Org. Chem. 2003, 68, 920; (c) Asao, N.; Yudha, S. S.; Nogami, T.; Yamamoto, Y.
Angew. Chem., Int. Ed. 2005, 44, 5526; (d) Asao, N.; Iso, K.; Yudha, S. S. Org. Lett.
2006, 8, 4149; (e) Yanada, R.; Obika, S.; Kono, H.; Takemoto, Y. Angew. Chem., Int.
Ed. 2006, 45, 3822; (f) Obika, S.; Kono, H.; Yasui, Y.; Yanada, R.; Takemoto, Y.
J. Org. Chem. 2007, 72, 4462.
13. CCDC 715241 (5d) contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from the Cambridge Crys-
tallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK, fax: þ44 (0)1223 336033, or e-mail: deposit@ccdc.cam.ac.uk.
100 MHz):
d 203.8, 136.1, 130.9, 128.9, 128.8, 128.6, 128.3, 128.2,
128.0, 127.1, 126.8, 116.2, 98.9, 48.3, 47.3, 38.8; HRMS-ESI-TOF:
calcd for C24H21NO2SNa ([MþNa]þ): 410.1191, found: 410.1211.
Acknowledgements
We thank the NNSF of China, NSF of Shanghai, 973 program
(2009CB825300), and Shanghai Leading Academic Discipline Pro-
ject for financial support (B108).
References and notes
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