An efficient synthesis of polysubstituted naphthalene derivatives by gold-catalyzed cyclization of 1-arylalka-2,3-dienyl acetates

Article abstract of DOI:10.1002/ejoc.201001112

An efficient synthetic strategy to generate differently polysubstituted naphthalenes and iodonaphthalenes through a gold-catalyzed cyclization reaction of 1-arylalka-2,3-dienyl acetates was described. Due to the substituent loading capability of both the

Full text of DOI:10.1002/ejoc.201001112

FULL PAPER
DOI: 10.1002/ejoc.201001112
An Efficient Synthesis of Polysubstituted Naphthalene Derivatives by
Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
Wangqing Kong,[a] Chunling Fu,[a] and Shengming Ma*[a]
Dedicated to Professor Barluenga on the occasion of his 70th birthday
Keywords: Allenes / Naphthalene / Gold / Cyclization / Reaction mechanisms
An efficient synthetic strategy to generate differently poly-
substituted naphthalenes and iodonaphthalenes through a
gold-catalyzed cyclization reaction of 1-arylalka-2,3-dienyl
acetates was described. Due to the substituent loading capa-
bility of both the aromatic ring and the allene moiety, dif-
ferent substituents may be introduced to the different loca-
tions of the naphthalenes. A possible mechanism of the reac-
tion involving the formation of alkenyl and naphthyl Au spe-
cies was proposed on the basis of the mechanistic study.
Iodination of the gold species afforded iodonaphthalenes,
which are useful building blocks to introduce molecular com-
plexity and diversity by coupling reactions.
tions[4] or coupling reactions.[5,6] Other important methods
include cyclic alkylation of γ-aryl-α,β-unsaturated carbonyl
compounds a (Scheme 1),[7] rearrangement of 4-hydroxycy-
clobut-2-enones b,[8] reactions of aryl halides or aryl metal
compounds c with two molecules of alkynes,[9] reactions of
highly reactive benzynes d with two molecules of alkynes,[10]
palladium-catalyzed annulation of alkynes with 1-phen-
ylalken-2-yl iodides/triflates e,[11] annulations via Fischer
carbenes f with alkynes,[12] annulation of α-aryl-substituted
carbonyl compounds g with alkynes,[13] and so on[14]
(Scheme 1). Although there are many useful synthetic
Introduction
Differently substituted naphthalene derivatives have played
an important role in the chemical and pharmaceutical in-
dustries[1] as well as in the fields of optical and electronic
materials.[2] The development of new and efficient method-
ologies for the synthesis of polysubstituted naphthalene de-
rivatives has recently attracted much attention.[3] Tradition-
ally, the regioselective construction of polysubstituted aro-
matic compounds has been carried out by the stepwise in-
troduction of substituents through electrophilic substitu-
Scheme 1. Known methodologies for the synthesis of polysubstituted naphthalene.
[a] Laboratory of Molecular Recognition and Synthesis,
Depatment of Chemistry, Zhejiang University,
routes to naphthalenes, the mild, efficient, regiocontrolled,
Hangzhou 310027, Zhejiang, People’s Republic of China
Fax: +86-216-260-9305
and diversified preparation of these compounds with spe-
cific substitution patterns remains a significant challenge to
synthetic organic chemists.
E-mail: masm@mail.sioc.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201001112.
Eur. J. Org. Chem. 2010, 6545–6555
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6545

W. Kong, C. Fu, S. Ma
FULL PAPER
On the other hand, recently, we reported a PtCl2-cata-
lyzed intramolecular cyclization reaction of 1-(indol-2-yl)-
2,3-allenols to afford carbazole derivatives (Scheme 2).[15]
On the basis of these results, we wondered whether naphth-
alene derivatives could be afforded by using arenes instead
of indoles as the starting point (Scheme 2).[16] Due to the
substituent loading capability of both the aromatic ring and
the allene moiety, this type of method will be of high diver-
sity. In this area, Lee et al. reported a Au-catalyzed cycliza-
tion of 1-aryl-(2-ethoxycarbonyl)butadienols for the synthe-
sis of naphthalenes.[17] Ohno[18] and Gagné[19] et al. also
reported the Au-catalyzed cyclization of N-alkoxycarbon-
ylallenylaniline and 6-arylhexadienes to afford dihydro-
quinolines and benzocyclohexanes, respectively. In this
paper, we wish to report our recent observation on the ef-
ficient synthesis of naphthalene and iodonaphthalene deriv-
atives from the readily available 1-aryl-alka-2,3-dienyl acet-
ates through a mechanism different from our previous
study.[15]
Scheme 3. Pt2+ or Au+/Ag+-catalyzed cyclization of allenol 1a.
NMR yield, and the reaction in toluene became compli-
cated (Table 1, Entries 6 and 7). In addition, it should be
noted that with the catalyst used by Lee et al.,[17] the reac-
tion of acetate 2a is complicated (Table 1, Entry 8).
Table 1. Optimization of the reaction conditions for the naphth-
alene-formation reaction of 1-(2,5-dimethoxyphenyl)-2-phen-
ylbuta-2,3-dienyl acetate (2a).[a]
Scheme 2. Cyclization of 2,3-allenols for the formation of the benz-
ene ring.
Entry
Catalyst
Solvent
Time
[h]
NMR yield
of 3a [%][b]
[c]
1
2
3
4
5
6
7
8
AuCl3
PtCl2
dioxane
dioxane
dioxane
dioxane
dioxane
CH3CN
toluene
CH2Cl2
19.6
[d]
[e]
Results and Discussion
AuCl(PPh3)/AgOTf
AuCl(PPh3)/AgSbF6
AuCl(PPh3)/AgBF4
AuCl(PPh3)/AgBF4
AuCl(PPh3)/AgBF4
AuCl(PPh3)/AgBF4
11.5
11.5
4
10
12
17
56
Initially, we tried the cyclization of 1-(2,5-dimeth-
oxyphenyl)-2-phenylbuta-2,3-dienol (1a) with PtCl2 as the
catalyst;[15] however, 1a was recovered (Scheme 3). With
AuCl(PPh3) and AgOTf as the catalyst used by Lee et al.,[16]
the reaction did occur; however, the cycloisomerization
product, that is, 2,5-dihydrofuran, instead of the corre-
sponding naphthalene derivatives 1,4-dimethoxy-6-phenyl-
naphthalene (3a) was formed obviously due to the higher
nucleophilicity of the hydroxy oxygen atom.[20] Thus, in or-
der to prevent the cycloisomerization involving the hydroxy
group, this functionality was protected in the form of acet-
ate to test this type of transformation.
82 (77)[f]
[g]
[h]
[h]
12
[a] The reaction was conducted with 2a (0.2 mmol) and the catalyst
(5 mol-%) at room temperature. [b] 1H NMR yield obtained by
using CH2Br2 as the internal standard. [c] The recovery of 2a was
86%. [d] Room temperature, 1.3 h; 80 °C, 17 h. [e] The recovery of
2a was 32%. [f] Isolated yield. [g] The recovery of 2a was 79 %.
[h] A complicated reaction mixture was formed.
Luckily, the reaction of acetate 2a in 1,4-dioxane with
With the optimized reaction conditions in hand, the
AuCl(PPh3) and AgOTf as the catalyst gave desired product scope of this Au-catalyzed cyclization reaction of acetates 2
3a, albeit in only 17% yield (Table 1, Entry 3). It should be was studied. Substituents on the phenyl ring could be 2,5-
[15]
noted that the starting material was recovered with PtCl2
dimethoxy, 3,4-methylenedioxy, 3,4-dimethoxy, and 3,4,5-
or AuCl3 as the catalyst (Table 1, Entries 1 and 2). Then, trimethoxy, affording the corresponding naphthalenes in
several combinations of AuCl(PPh3) with different silver good yields. The R6 group could be phenyl and alkyl. It is
salts were tested, among which AgBF4 turned out to be noteworthy that this reaction shows an interesting exclusive
the best, affording product 3a in 82% NMR yield (Table 1, elimination of the OAc group to form the naphthalene ring
Entries 3–5). Notably, the solvent effect is obvious, as the even when R6 is CH2OEt or CH2OAc (Table 2, Entries 6
reaction in CH3CN led to recovery of substrate 2a in 79% and 7).
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Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
Table 2. Synthesis of naphthalene derivatives through gold-cata- the allene moiety, which excludes the mechanism involving
lyzed cyclization of 1-aryl-alka-2,3-dienyl acetates.[a]
M2 (Scheme 5). This observation prompted us to quench
the reaction with I+. In fact, β-iodonaphthalene derivative
4c was afforded in 62% NMR yield with 15% NMR yield
of 3c when the reaction was conducted in the presence of
NIS (Scheme 6).[22] It should be noted that the reaction of
2a with 1.0 equiv. of NIS in dioxane did not proceed.
Entry
2
Time Yield
[h] of 3 [%]
R1
R2
R3; R4; R5
R6
1
2
3
4
5
6
7
8
9
MeO
MeO
H
H
H; MeO; H
H; MeO; H
H; H; H
H; H; H
H; H; H
H; H; H
H; H; H
H; H; H
Ph (2a)
nBu (2b)
Ph (2c)
4
77 (3a)
19 87 (3b)
11 85 (3c)
9
6
12
17 84 (3g)
19 84 (3h)
12
17
–OCH2O–
–OCH2O–
–OCH2O–
–OCH2O–
–OCH2O–
MeO MeO
nBu (2d)
89 (3d)
86 (3e)
74 (3f)
p-MeC6H5 (2e)
CH2OEt (3f)
CH2OAc (3g)
Ph (2h)
MeO MeO MeO; H; H
–OCH2O– H; H; n-hexyl
nBu (2i)
Me (2j)
80 (3i)
61 (3j)
10
[a] A solution of 2, AuCl(PPh3) (5 mol-%), and AgBF4 (5 mol-%)
was stirred in 1,4-dioxane at room temperature.
Scheme 6. The reaction in the presence of D2O and NIS.
We were not satisfied with the results of the β-iodo-
naphthalene formation. Therefore, 2c was used as the model
substrate to optimize the conditions with some typical re-
sults listed in Table 3. Initially, the yield of 4c was improved
to 72% with 1.5 equiv. of NIS (Table 3, Entry 2); however,
the yield of 4c was lower when 2.0 equiv. of NIS was ap-
plied (Table 3, Entry 3); similar results were observed in
acetone (Table 3, Entry 7), better than those in other sol-
vents such as THF, DMF, Et2O, and so on (Table 3, En-
tries 4–6); to improve the selectivity of iodonolysis versus
protonolysis, the reaction was conducted at 0 °C in acetone,
and the best yield (77%) and selectivity (94:6) were achieved
(Table 3, Entry 8); no better results was obtained at –20 °C
or with more NIS (Table 3, Entries 9 and 10). Thus, we de-
Relatively electron-rich aryl groups are required, as the
reaction of 2k or 2l failed to proceed (Scheme 4). A mecha-
nism involving metal carbene intermediate M2[21] was pro-
posed (Scheme 5).
Table 3. Optimization of the reaction conditions for the β-iodo-
naphthalene formation reaction from 2c.
Scheme 4. The electronic effect of the substituents on the aromatic
ring.
Entry
NIS
[equiv.]
Solvent
T
[°C]
Time
[h]
Yield of Ratio of
4c [%][a]
4c/3c
1
2
3
4
5
6
7
8
9
1.0
1.5
2.0
1.5
1.5
1.5
1.5
1.5
1.5
2.0
dioxane
dioxane
dioxane
THF
Et2O
DMF
acetone
acetone
acetone –20
acetone
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
0
7
11
17
19.5
19.5
19.5
10.5
21
22
15
62
72
66
56
81:19
86:14
81:19
84:16
83:17
20
[b]
64
77
71
64
91:9
94:6
93:7
94:6
Scheme 5. Two proposed mechanisms.
10
0
However, when D2O was added to the reaction mixture,
the reaction proceeded smoothly to afford [D1]-3c in 42%
yield with 42% D-incorporation at the central carbon of vered in 99% yield.
1
[a] NMR yield determined by H NMR spectroscopic analysis by
using CH2Br2 as the internal standard. [b] Compound 2c was reco-
Eur. J. Org. Chem. 2010, 6545–6555
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6547

W. Kong, C. Fu, S. Ma
FULL PAPER
fined the experimental protocol for the cyclization of 1-aryl- Table 4. Synthesis of β-iodonaphthalene derivatives by gold-cata-
lyzed cyclization of 1-arylalka-2,3-dienyl acetates and subsequent
Sonogashira coupling reaction with propargyl alcohol.
alka-2,3-dienyl acetates under the catalysis of 5 mol-% of
AuCl(PPh3)/AgBF4 and 1.5 equiv. of NIS in acetone at 0 °C
as the standard reaction conditions to afford β-iodo-
naphthalenes (Table 3, Entry 8).
β-Iodonaphthalenes 4a, 4g, and 4i were then easily syn-
thesized under the standard conditions (Scheme 7).
Entry Substrate Time 1 Yield of Ratio
Time 2 Yield of
[h]
[h]
4 [%][a]
of 4/3
5 [%][b]
1
2
3
4
5
6
7
8
9
2a
2b
2c
2d
2e
2f
2g
2h
2i
11
12
21
12
16
14
11
12
11
84 (4a)
79 (4b)
77 (4c)
89 (4d)
89 (4e)
71 (4f)
62 (4g)
71 (4h)
62 (4i)
100:0
94:6
94:6
95:5
95:5
96:4
100:0
91:9
100:0
31
14
24
18
14
23
11
37.5
32
58 (5a)
53 (5b)
61 (5c)
67 (5d)
52 (5e)
47 (5f)
48 (5g)
43 (5h)
48 (5i)
1
[a] NMR yield determined by H NMR spectroscopic analysis by
using CH2Br2 as the internal standard. [b] Combined isolated
yields of two steps from 2.
Scheme 7. The reaction in the presence of NIS.
On the basis of these results, we proposed a possible
mechanism for the reaction, which is different from that
proposed for the similar cyclization of 1-(indol-2-yl)-2,3-all-
enols.[15] β-Naphthyl gold intermediate M3 was formed by
elimination of acetic acid from six-membered cyclohexenyl
gold species M1. Finally, protonolysis or iodonolysis re-
leased the gold catalyst into the catalytic cycle and afforded
target naphthalene 3a or iodonaphthalene 4a, respectively
(Scheme 5). The reaction of some substrates afforded 4 to-
gether with a very minor amount of 3, which could not
be separated by chromatography on silica gel. Thus, all the
iodonaphthalenes were further converted into 3-(naphth-
Transformations of 4a by Suzuki coupling with different
boronic acids and Sonogashira cross-coupling with other
terminal alkynes, leading to the formation 6a, 7a, 8a, and
9a in yields of 73–91%, were further demonstrated to show
the synthetic potential of these cyclization products
(Scheme 8).[23]
Conclusions
In summary, we have developed an efficient method to
alen-2-yl)prop-2-yn-1-ol derivatives by Sonogashira cou- generate naphthalene and β-iodonaphthalene derivatives
pling with propargyl alcohol (Table 4).
through the simple intramolecular C-alkylation of 1-aryl-
Scheme 8. Pd-catalyzed cross-coupling strategy of 4a.
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Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
(75 MHz, CDCl3): δ = 208.7, 170.0, 147.7, 147.6, 133.6, 132.1,
128.4, 127.1, 126.6, 121.5, 108.0, 106.8, 101.1, 80.7, 73.1, 21.2 ppm.
buta-2,3-dienyl acetate catalyzed by 5 mol-% each of
AuCl(PPh3) and AgBF4. A possible mechanism of the reac-
tion was proposed on the basis of the mechanistic studies.
Due to the easy availability of the starting materials,[24] mild
reaction conditions (room temperature), and potential of
the products, this method may be useful in organic synthe-
sis, material science, and medicinal chemistry.
IR (neat): ν = 2901, 1942, 1742, 1598, 1504, 1489, 1445, 1369, 1227,
˜
1099, 1038 cm–1. MS (70 eV, EI): m/z (%) = 308 (16.20) [M]+, 266
(100). HRMS: calcd. for C19H16O4 [M]+ 308.1049; found 308.1056.
1-(Benzo[d][1,3]dioxol-5-yl)-2-vinylidenehexyl Acetate (2d): Accord-
ing to the general procedure, the reaction of 1d (0.4901 g, 2 mmol),
Et3N (1 mL), DMAP (49.6 mg, 0.41 mmol), and Ac2O (0.7201 g,
7.1 mmol) in Et2O (10 mL) afforded 2d (0.3400 g, 59%) after
chromatography (petroleum ether/ethyl acetate, 20:1) as a liquid.
1H NMR (300 MHz, CDCl3): δ = 6.88–6.80 (m, 2 H, ArH), 6.76
(d, J = 8.1 Hz, 1 H, ArH), 6.04 (t, J = 2.7 Hz, 1 H, CHOAc), 6.00–
5.90 (m, 2 H, OCH2O), 4.86 (q, J = 3.1 Hz, 2 H, CH2=), 2.08 (s,
3 H, COCH3), 1.90–1.78 (m, 2 H), 1.45–1.20 (m, 4 H), 0.85 (t, J =
7.2 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 205.5,
169.9, 147.6, 147.4, 132.4, 121.1, 107.9, 107.7, 104.5, 101.1, 78.6,
Experimental Section
Synthesis of 1-(2,5-Dimethoxyphenyl)-2-phenylbuta-2,3-dienyl Acet-
ate (2a) as a Representative General Procedure for the Preparation
of 1-Aryl-alka-2,3-dienyl Acetates 2a–j: To a dried one-neck round-
bottomed flask equipped with a magnetic stir bar were added 1a
(0.5645 g, 2.0 mmol), Et3N (0.5 mL), DMAP (49.5 mg,
0.41 mmol), and dry Et2O (8 mL). To this stirred solution was
added Ac2O (0.7524 g, 7.4 mmol), and the resulting mixture was
stirred at room temperature until the reaction was complete as
monitored by TLC. The reaction was quenched with saturated
aqueous NaHCO3. The aqueous layer was extracted with diethyl
ether (3ϫ15 mL), and the combined organic layers were washed
with water and dried with anhydrous Na2SO4. Following filtration
and evaporation, the residue was purified by silica gel column
chromatography (petroleum ether/ethyl acetate, 10:1) to give 2a
(0.5421 g, 84%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.43–
7.34 (m, 2 H, ArH), 7.32–7.23 (m, 2 H, ArH), 7.22–7.13 (m, 2 H,
ArH), 6.99 (d, J = 2.1 Hz, 1 H, CHOAc), 6.84–6.74 (m, 2 H, ArH),
5.19–5.08 (m, 2 H, CH2=), 3.79 (s, 3 H, OCH3), 3.73 (s, 3 H,
OCH3), 2.08 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
208.9, 169.9, 153.4, 151.0, 133.9, 128.3, 127.9, 127.0, 126.4, 114.5,
75.3, 29.4, 27.9, 22.3, 21.2, 13.9 ppm. IR (neat): ν = 2957, 2930,
˜
2877, 1959, 1743, 1504 1489, 1444, 1369, 1231, 1099, 1040 cm–1.
MS (70 eV, EI): m/z (%) = 288 (13.27) [M]+, 189 (100). HRMS:
calcd. for C17H20O4 [M]+ 288.1362; found 288.1360.
1-(Benzo[d][1,3]dioxol-5-yl)-2-p-tolylbuta-2,3-dienyl Acetate (2e):
According to the general procedure, the reaction of 1e (1.4257 g,
5.1 mmol), Et3N (2.5 mL), DMAP (125.1 mg, 1.0 mmol), and
Ac2O (1.9102 g, 18.7 mmol) in Et2O (20 mL) afforded 2e (1.1896 g,
73%) after chromatography (petroleum ether/ethyl acetate, 80:1–
1
40:1) as a solid; m.p. 66–68 °C (ethyl acetate/n-hexane). H NMR
(300 MHz, CDCl3): δ = 7.23 (d, J = 8.7 Hz, 2 H, ArH), 7.07 (d, J
= 8.4 Hz, 2 H, ArH), 6.92 (d, J = 8.4 Hz, 2 H, ArH), 6.74 (d, J =
8.7 Hz, 1 H, ArH), 6.70–6.63 (m, CHOAc), 5.92 (s, 2 H, OCH2O),
5.19 (d, J = 2.1 Hz, 2 H, CH2=), 2.28 (s, 3 H, COCH3), 2.08 (s, 3
H, ArCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 208.4, 169.9,
147.6, 147.5, 136.8, 132.1, 130.5, 129.1, 126.5, 121.5, 108.01,
113.4, 111.6, 106.8, 80.6, 67.4, 56.2, 55.6, 21.1 ppm. IR (neat): ν =
˜
2940, 2835, 1943, 1743, 1597, 1499, 1464, 1431, 1371, 1280, 1227,
1179, 1158, 1047, 1026 cm–1. MS (70 eV, EI): m/z (%) = 324 (5.41)
[M]+, 251 (100). HRMS: calcd. for C20H20O4 [M]+ 324.1362; found
324.1359.
107.99, 106.6, 101.1, 80.5, 73.1, 21.2, 21.0 ppm. IR (neat): ν = 2897,
˜
1942, 1742, 1606, 1504, 1489, 1445, 1369, 1229, 1099, 1038 cm–1.
MS (70 eV, EI): m/z (%) = 322 (7.86) [M]+, 280 (100). C20H18O4
(322.36): calcd. C 74.52, H 5.63; found C 74.45, H 5.50.
1-(2,5-Dimethoxyphenyl)-2-vinylidenehexyl Acetate (2b): According
to the general procedure, the reaction of 1b (1.5410 g, 5.9 mmol),
Et3N (3.4 mL), DMAP (143.2 mg, 11.7 mmol), and Ac2O (2.2 mL,
d = 1.082 g/mL, 2.3804 g, 23 mmol) in Et2O (40 mL) afforded 2b
(1.4970 g, 84%) after chromatography (petroleum ether/ethyl acet-
1-(Benzo[d][1,3]dioxol-5-yl)-2-(ethoxymethyl)buta-2,3-dienyl Acetate
(2f): According to the general procedure, the reaction of 1f
(0.6011 g, 2.4 mmol), Et3N (0.5 mL), DMAP (25.0 mg, 0.2 mmol),
and Ac2O (0.9125 g, 8.9 mmol) in Et2O (10 mL) afforded 2f
(0.5887 g, 84%) after chromatography (petroleum ether/ethyl acet-
1
1
ate = 10:1) as a liquid. H NMR (300 MHz, CDCl3): δ = 6.95 (t,
ate, 20:1–10:1) as a liquid. H NMR (300 MHz, CDCl3): δ = 6.92–
J = 1.5 Hz, 1 H, ArH), 6.85–6.75 (m, 2 H, ArH), 6.55 (t, J =
2.7 Hz, 1 H, CHOAc), 4.78 (q, J = 2.7 Hz, 2 H, CH2=), 3.78 (s, 3
H, OCH3), 3.77 (s, 3 H, OCH3), 2.09 (s, 3 H, COCH3), 1.98–1.83
(m, 2 H), 1.48–1.20 (m, 4 H), 0.86 (t, J = 7.2 Hz, 3 H, CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 206.0, 169.9, 153.4, 151.1, 128.2,
114.1, 113.2, 111.7, 104.3, 78.3, 69.3, 56.2, 55.7, 29.5, 28.2, 22.2,
6.83 (m, 2 H, ArH), 6.76 (d, J = 4.5 Hz, 1 H, ArH), 6.19 (t, J =
2.7 Hz, 1 H, CHOAc), 5.97–5.92 (m, 2 H, OCH2O), 4.91 (d, J =
2.7 Hz, 2 H, CH2=), 3.98 (dt, J = 12.0, 2.7 Hz, 1 H, CH2O), 3.86
(dt, J = 12.0, 2.7 Hz, 1 H, CH2O), 3.57–3.30 (m, 2 H, OCH2CH3),
2.07 (s, 3 H, COCH3), 1.16 (t, J = 6.9 Hz, 3 H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 206.2, 169.8, 147.6, 147.5, 132.0,
121.2, 107.9, 107.8, 102.1, 101.1, 78.4, 73.0, 68.8, 65.2, 21.1,
21.2, 13.9 ppm. IR (neat): ν = 2956, 2931, 2836, 1959, 1743, 1591,
˜
1501, 1465, 1430, 1370, 1280, 1230, 1179, 1159, 1049, 1027 cm–1.
MS (70 eV, EI): m/z (%) = 304 (11.27) [M]+, 231 (100). HRMS:
calcd. for C18H24O4 [M]+ 304.1675; found 304.1677.
15.0 ppm. IR (neat): ν = 2976, 2894, 1959, 1744, 1610, 1504, 1489,
˜
1445, 1370, 1232, 1096, 1039 cm–1. MS (70 eV, EI): m/z (%) = 290
(6.95) [M]+, 151 (100). HRMS: calcd. for C16H18O5 [M]+ 290.1154;
found 290.1154.
1-(Benzo[d][1,3]dioxol-5-yl)-2-phenylbuta-2,3-dienyl Acetate (2c):
According to the general procedure, the reaction of 1c (2.6615 g,
1-(Benzo[d][1,3]dioxol-5-yl)-2-vinylidenepropane-1,3-diyl Diacetate
10 mmol), Et3N (5 mL), DMAP (244.1 mg, 2 mmol), and Ac2O (2g): According to the general procedure, the reaction of 1g
(4 mL, d = 1.082 g/mL, 4.3280 g, 42.4 mmol) in Et2O (40 mL) af-
forded 2c (2.0649 g, 67%) after chromatography (petroleum ether/
ethyl acetate, 10:1) as a liquid. H NMR (300 MHz, CDCl3): δ =
(0.3764 g, 1.7 mmol), Et3N (0.5 mL), DMAP (42.5 mg,
0.35 mmol), and Ac2O (0.6752 g, 6.6 mmol) in Et2O (8 mL) af-
forded 2g (0.4041 g, 78%) after chromatography (petroleum ether/
1
1
7.38–7.30 (m, 2 H, ArH), 7.29–7.22 (m, 2 H, ArH), 7.21–7.13 (m,
ethyl acetate, 10:1) as a liquid. H NMR (300 MHz, CDCl3): δ =
1 H, ArH), 6.96–6.88 (m, 2 H, ArH), 6.78–6.71 (m, 1 H, ArH), 6.87–6.82 (m, 2 H, ArH), 6.76 (d, J = 8.4 Hz, 1 H, ArH), 6.20 (t,
6.68 (t, J = 2.6 Hz, 1 H, CHOAc), 5.92 (s, 2 H, OCH2O), 5.22 (d,
J = 2.7 Hz, 1 H, CHOAc), 5.96 (s, 2 H, OCH2O), 4.98 (q, J =
2.4 Hz, 2 H, CH2=), 4.61 (dt, J = 12.3, 2.1 Hz, 1 H, CH2O), 4.45
J = 2.4 Hz, 2 H, CH2=), 2.08 (s, 3 H, COCH3) ppm. 13C NMR
Eur. J. Org. Chem. 2010, 6545–6555
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6549

W. Kong, C. Fu, S. Ma
FULL PAPER
(dt, J = 12.3, 2.1 Hz, 1 H, CH2OAc), 2.09 (s, 3 H, COCH3), 2.02 7.45–7.35 (m, 1 H, ArH), 6.75 (d, J = 8.4 Hz, 1 H, ArH), 6.71 (d,
(s, 3 H, COCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 207.0, J = 8.4 Hz, 1 H, ArH), 4.00 (s, 3 H), 3.99 (s, 3 H, OCH3) ppm. 13
170.5, 169.7, 147.63, 147.56, 131.5, 121.0, 107.9, 107.6, 101.1, NMR (75 MHz, CDCl3): δ = 149.7, 149.4, 141.3, 138.4, 128.7,
C
100.7, 79.3, 72.9, 62.0, 21.0, 20.7 ppm. IR (neat): ν = 1961, 1743, 127.4, 127.2, 126.5, 125.4, 125.3, 122.4, 119.8, 103.6, 103.2,
˜
1504, 1489, 1445, 1374, 1232, 1098, 1037 cm–1. MS (70 eV, EI): m/z
(%) = 305 (0.73) [M + 1]+, 304 (4.06) [M]+, 43 (100). HRMS: calcd.
for C16H16O6 [M]+ 304.0947; found 304.0946.
55.7 ppm. IR (neat): ν = 2991, 2936, 2832, 1629, 1599, 1494, 1463,
˜
1422, 1394, 1363, 1272, 1236, 1165, 1104, 1042, 1001 cm–1. MS
(70 eV, EI): m/z (%) = 265 (14.88) [M + 1]+, 264 (75.57) [M]+,
249 (100) [M]+. HRMS: calcd. for C18H16O2 [M]+ 264.1150; found
264.1151.
1-(3,4-Dimethoxyphenyl)-2-phenylbuta-2,3-dienyl Acetate (2h): Ac-
cording to the general procedure, the reaction of 1h (1.0012 g,
3.6 mmol), Et3N (1 mL), DMAP (86.4 mg, 0.71 mmol), and Ac2O
6-Butyl-1,4-dimethoxynaphthalene (3b): According to the general
(1.2912 g, 12.7 mmol) in Et2O (15 mL) afforded 2h (0.9508 g, 83%) procedure, the reaction of AuCl(PPh3) (7.5 mg, 0.015 mmol),
after chromatography (petroleum ether/ethyl acetate, 10:1) as a li-
quid. H NMR (300 MHz, CDCl3): δ = 7.39–7.32 (m, 2 H, ArH),
7.31–7.23 (m, 2 H, ArH), 7.22–7.14 (m, 1 H, ArH), 7.01 (dd, J =
8.4, 1.8 Hz, 1 H, ArH), 6.95 (d, J = 1.8 Hz, 1 H, ArH), 6.81 (d, J
= 8.4 Hz, 1 H, ArH), 6.73 (t, J = 2.4 Hz, 1 H, CHOAc), 5.20 (d, J
AgBF4 (3.2 mg, 0.016 mmol), and 2b (90.7 mg, 0.3 mmol) in diox-
ane (1.5 mL) at room temperature for 19 h afforded 3b (63.1 mg,
87%) after chromatography (petroleum ether/ethyl acetate, 60:l) as
a liquid. H NMR (300 MHz, CDCl3): δ = 8.17 (d, J = 8.7 Hz, 1
H, ArH), 8.04 (d, J = 0.9 Hz, 1 H, ArH), 7.40 (dd, J = 8.6, 1.7 Hz,
1
1
= 2.7 Hz, 2 H, CH2=), 3.86 (s, 6 H, OCH3), 2.10 (s, 3 H, 1 H, ArH), 6.70 (d, J = 8.4 Hz, 1 H, ArH), 6.66 (d, J = 8.4 Hz, 1
COCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 208.8, 170.1,
H, ArH), 3.99 (s, 3 H, OCH3), 3.97 (s, 3 H, OCH3), 2.83 (t, J =
7.8 Hz, 2 H), 1.82–1.66 (m, 2 H), 1.54–1.32 (m, 2 H), 0.99 (t, J =
149.0, 148.8, 133.8, 130.6, 128.4, 127.1, 126.6, 120.3, 110.8, 110.7,
106.9, 80.6, 73.2, 55.83, 55.79, 21.2 ppm. IR (neat): ν = 2936, 2836, 7.4 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.5,
˜
1942, 1740, 1595, 1517, 1496, 1464, 1452, 1420, 1370, 1231, 1155,
149.1, 140.6, 127.3, 126.4, 124.7, 121.7, 120.2, 103.1, 102.1, 55.6,
1140, 1027 cm–1. MS (70 eV, EI): m/z (%) = 324 (2.68) [M]+, 264 36.0, 33.7, 22.4, 14.0 ppm. IR (neat): ν = 2997, 2954, 2931, 2857,
˜
(100). HRMS: calcd. for C20H20O4 [M]+ 324.1362; found 324.1362. 2833, 1633, 1603, 1510, 1463, 1426, 1369, 1271, 1243, 1210, 1194,
1162, 1098, 1006 cm–1. MS (70 eV, EI): m/z (%) = 245 (11.70) [M
1-(3,4,5-Trimethoxyphenyl)-2-vinylidenehexyl Acetate (2i): Accord-
ing to the general procedure, the reaction of 1i (0.8474 g,
2.9 mmol), Et3N (1 mL), DMAP (70.0 mg, 0.57 mmol), and Ac2O
+ 1]+, 244 (65.88) [M]+, 229 (100) [M]+. HRMS: calcd. for
C16H20O2 [M]+ 244.1463; found 244.1462.
(1.1012 g, 10.8 mmol) in Et2O (10 mL) afforded 2i (0.8564 g, 88%)
after chromatography (petroleum ether/ethyl acetate, 10:1) as a li-
quid. 1H NMR (300 MHz, CDCl3): δ = 6.58 (s, 2 H, ArH), 6.07
(t, J = 2.4 Hz, 1 H, CHOAc), 4.87 (q, J = 3.0 Hz, 2 H, CH2=),
7-Phenylnaphtho[2,1-d][1,3]dioxole (3c): According to the general
procedure, the reaction of AuCl(PPh3) (7.5 mg, 0.015 mmol),
AgBF4 (3.5 mg, 0.018 mmol), and 2c (90.5 mg, 0.29 mmol) in diox-
ane (2 mL) at room temperature for 11 h afforded 3c (61.7 mg,
3.859 (s, 3 H, OCH3), 3.857 (s, 3 H, OCH3), 3.834 (s, 3 H, OCH3), 85%) after chromatography (petroleum ether/ethyl acetate, 100:l)
2.11 (s, 3 H, COCH3), 1.92–1.79 (m, 2 H), 1.45–1.20 (m, 4 H), 0.85
(t, J = 7.1 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
205.6, 170.0, 153.0, 137.8, 133.9, 104.5, 104.3, 78.6, 75.5, 60.7, 56.1,
as a solid; m.p. 138–139 °C (diethyl ether/n-hexane). 1H NMR
(300 MHz, CDCl3): δ = 7.90 (d, J = 1.2 Hz, 1 H, ArH), 7.80–7.69
(m, 3 H, ArH), 7.63 (dd, J = 8.4, 1.8 Hz, 1 H, ArH), 7.58–7.46 (m,
2 H, ArH), 7.45–7.35 (m, 1 H, ArH), 7.18 (d, J = 8.4 Hz, 2 H,
ArH), 6.05 (s, 2 H, OCH2O) ppm. 13C NMR (75 MHz, CDCl3): δ
29.4, 27.9, 22.2, 21.2, 13.8 ppm. IR (neat): ν = 2967, 2935, 2873,
˜
2839, 1958, 1744, 1592, 1506, 1463, 1421, 1371, 1332, 1232, 1128,
1012 cm–1. MS (70 eV, EI): m/z (%) = 334 (2.28) [M]+, 274 (100). = 147.8, 147.6, 141.1, 137.1, 130.7, 129.6, 128.7, 127.4, 127.2, 127.1,
HRMS: calcd. for C19H26O5 [M]+ 334.1780; found 334.1782.
125.0, 123.9, 104.1, 103.6, 101.0 ppm. IR (KBr): ν = 2934, 2831,
˜
1625, 1579, 1498, 1459, 1413, 1322, 1274, 1237, 1107, 1091 cm–1.
MS (70 eV, EI): m/z (%) = 249 (18.73) [M + 1]+. 248 (100) [M]+.
C17H12O2 (248.28): calcd. C 82.26, H 4.84; found C 82.24, H 4.99.
1-(Benzo[d][1,3]dioxol-5-yl)-2-methyldeca-2,3-dienyl Acetate (2j):
According to the general procedure, the reaction of 1j (0.8654 g,
3.0 mmol), Et3N (1 mL), DMAP (74.9 mg, 0.61 mmol), and Ac2O
(1.0210 g, 10.0 mmol) in Et2O (10 mL) afforded 2j (0.7566 g, 77%)
after chromatography (petroleum ether/ethyl acetate, 40:1) as a li-
7-Butylnaphtho[2,1-d][1,3]dioxole (3d): According to the general
procedure, the reaction of AuCl(PPh3) (7.4 mg, 0.015 mmol),
AgBF4 (3.1 mg, 0.015 mmol), and 2d (87.1 mg, 0.3 mmol) in diox-
ane (2 mL) at room temperature for 9 h afforded 3d (61.2 mg, 89%)
1
quid. H NMR (300 MHz, CDCl3): δ = 6.90–6.70 (m, 3 H, ArH),
6.02 (dd, J = 6.9, 2.1 Hz, 1 H, CHOAc), 5.96–5.89 (m, 2 H,
OCH2O), 5.30–5.10 (m, 1 H, CH=), 2.08 (s, 3 H, COCH3), 2.10–
1.90 (m, 2 H), 1.59 (t, J = 2.6 Hz, 3 H, CH3), 1.45–1.20 (m, 8 H), quid. H NMR (300 MHz, CDCl3): δ = 7.61 (d, J = 8.1 Hz, 1 H,
after chromatography (petroleum ether/ethyl acetate, 100:l) as a li-
1
0.88 (t, J = 6.8 Hz, 3 H, CH CH ) ppm. IR (neat): ν = 2961, 2927,
ArH), 7.47 (s, 1 H, ArH), 7.22 (d, J = 8.1 Hz, 1 H, ArH), 7.11 (d,
J = 7.2 Hz, 2 H, ArH), 6.02 (s, 2 H, OCH2O), 2.75 (t, J = 7.8 Hz,
˜
2
3
2856, 1961, 1744, 1606, 1504, 1489, 1444, 1368, 1232, 1097,
1040 cm–1. MS (70 eV, EI): m/z (%) = 330 (11.51) [M]+, 203 (100). 2 H), 1.78–1.62 (m, 2 H), 1.52–1.35 (m, 2 H), 1.00 (t, J = 7.4 Hz,
C20H26O4 (330.42): calcd. C 72.70, H 7.93; found C 72.89, H 8.10.
3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.5, 146.9,
138.9, 130.6, 128.6, 126.8, 125.7, 103.6, 103.5, 100.8, 35.6, 33.6,
Synthesis of 1,4-Dimethoxy-6-phenylnaphthalene (3a) as a Represen-
tative General Procedure for the Preparation of Naphthalenes 3a–j:
A dried Schlenk tube was charged with AuCl(PPh3) (4.9 mg,
0.01 mmol), AgBF4 (2.5 mg, 0.013 mmol), 2a (64.0 mg,
0.20 mmol), and dioxane (1 mL) sequentially under an atmosphere
of N2. After continuous stirring for 4 h at room temperature, the
reaction was complete as monitored by TLC. Evaporation and col-
umn chromatography on silica gel (petroleum ether/ethyl acetate,
22.4, 14.0 ppm. IR (neat): ν = 2958, 2925, 2856, 1618, 1495, 1466,
˜
1445, 1257, 1177, 1150, 1044. MS (70 eV, EI): m/z (%) = 229 (6.35)
[M + 1]+, 228 (39.25) [M]+, 185 (100). HRMS: calcd. for C15H16O2
[M]+ 228.1150; found 228.1152.
7-p-Tolylnaphtho[2,1-d][1,3]dioxole (3e): According to the general
procedure, the reaction of AuCl(PPh3) (7.2 mg, 0.015 mmol),
AgBF4 (3.1 mg, 0.015 mmol), and 2e (95.4 mg, 0.3 mmol) in diox-
ane (2 mL) at room temperature for 6 h afforded 3e (66.8 mg, 86%)
1
80:l) afforded 3a (40.0 mg, 77%) as a liquid. H NMR (300 MHz,
CDCl3): δ = 8.48 (d, J = 1.8 Hz, 1 H, ArH), 8.31 (d, J = 8.7 Hz, 1 after chromatography (petroleum ether/ethyl acetate, 80:l) as a so-
H, ArH), 7.86–7.75 (m, 3 H, ArH), 7.51 (t, J = 7.2 Hz, 2 H, ArH), lid; m.p. 152–153 °C (ethyl acetate/n-hexane). 1H NMR (300 MHz,
6550
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6545–6555

Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
CDCl3): δ = 7.83 (s, 1 H, ArH), 7.71 (d, J = 8.4 Hz, 1 H, ArH),
3.977 (s, 3 H, OCH3), 2.75 (t, J = 7.7 Hz, 2 H), 1.78–1.60 (m, 2
7.53–7.51 (m, 3 H, ArH), 7.27 (d, J = 8.4 Hz, 2 H, ArH), 7.15 (s, H), 1.49–1.30 (m, 2 H), 0.97 (t, J = 7.4 Hz, 3 H, CH3) ppm. 13C
1 H, ArH), 7.12 (s, 1 H, ArH), 6.03 (s, 2 H, OCH2O), 2.41 (s, 3 H, NMR (75 MHz, CDCl3): δ = 152.9, 147.9, 140.3, 140.1, 131.0,
ArCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.8, 147.5, 138.2, 125.2, 125.0, 122.6, 121.5, 101.9, 61.3, 61.1, 55.7, 35.7, 33.5, 22.3,
137.0, 136.8, 130.7, 129.5, 129.4, 127.3, 127.0, 124.7, 123.8, 104.0,
14.0 ppm. IR (neat): ν = 2956, 2932, 2857, 1629, 1605, 1576, 1502,
˜
103.6, 101.0, 21.1 ppm. IR (KBr): ν = 3024, 2913, 1618, 1507, 1494,
1480, 1465, 1411, 1393, 1336, 1252, 1203, 1130, 1105, 1040, 1003.
˜
1474, 1443, 1385, 1273, 1245, 1202, 1159, 1078, 1047. MS (70 eV,
MS (70 eV, EI): m/z (%) = 275 (19.24) [M + 1]+, 274 (100) [M]+.
EI): m/z (%) = 263 (19.40) [M + 1]+, 262 (100) [M]+. C18H14O2 HRMS: calcd. for C17H22O3 [M]+ 274.1569; found 274.1571.
(262.31): calcd. C 82.42, H 5.38; found C 82.51, H 5.46.
9-Hexyl-7-methylnaphtho[2,1-d][1,3]dioxole (3j): According to the
general procedure, the reaction of AuCl(PPh3) (7.1 mg,
0.014 mmol), AgBF4 (3.1 mg, 0.015 mmol), and 2j (99.1 mg,
0.3 mmol) in dioxane (2 mL) at room temperature for 17 h afforded
7-(Ethoxymethyl)naphtho[2,1-d][1,3]dioxole (3f): According to the
general procedure, the reaction of AuCl(PPh3) (7.3 mg,
0.015 mmol), AgBF4 (3.2 mg, 0.016 mmol), and 2f (69.1 mg,
0.3 mmol) in dioxane (1.5 mL) at room temperature for 12 h af-
3j (49.2 mg, 61%) after chromatography (petroleum ether/ethyl
1
forded 3f (40.3 mg, 74%) after chromatography (petroleum ether/
acetate, 100:l) as a liquid. H NMR (300 MHz, CDCl3): δ = 7.37–
ethyl acetate, 40:l) as a liquid. 1H NMR (300 MHz, CDCl3): δ =
7.28 (m, 2 H, ArH), 7.10–7.03 (m, 2 H, ArH), 6.03 (s, 2 H,
7.68–7.58 (m, 2 H, ArH), 7.33 (dd, J = 8.4, 1.8 Hz, 1 H, ArH),
OCH2O), 2.92 (t, J = 7.8 Hz, 2 H, ArCH2), 2.45 (s, 3 H, ArCH3),
7.11 (s, 2 H, ArH), 6.02 (s, 2 H, OCH2O), 4.62 (s, 2 H, ArCH2O),
1.79–1.65 (m, 2 H), 1.53–1.28 (m, 6 H), 0.93 (t, J = 7.1 Hz, 3 H,
CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.0, 146.9, 137.9,
133.5, 133.1, 126.77, 126.71, 124.8, 104.0, 100.8, 100.4, 33.6, 31.8,
3.58 (q, J = 7.0 Hz, 2 H, OCH2CH3), 1.28 (t, J = 7.0 Hz, 3 H,
CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 147.7, 147.5, 134.5,
130.3, 129.9, 127.1, 125.8, 124.4, 103.9, 103.7, 101.0, 72.8, 65.7,
30.7, 29.6, 22.7, 21.4, 14.1 ppm. IR (neat): ν = 2928, 1621, 1501,
˜
15.2 ppm. IR (neat): ν = 2974, 2864, 1618, 1498, 1467, 1444, 1371,
˜
1469, 1232, 1042. MS (70 eV, EI): m/z (%) = 271 (6.08) [M +
1]+, 270 (27.47) [M]+, 199 (100). HRMS: calcd. for C18H22O2
[M]+ 270.1620; found 270.1629.
1341, 1323, 1239, 1177, 1145, 1113, 1071, 1041. MS (70 eV, EI):
m/z (%) = 231 (8.68) [M + 1]+, 230 (55.75) [M]+, 185 (100). HRMS:
calcd. for C14H14O3 [M]+ 230.0943; found 230.0945.
Synthesis of Iodonaphthalenes 4
Naphtho[2,1-d][1,3]dioxol-7-ylmethyl Acetate (3g): According to the
general procedure, the reaction of AuCl(PPh3) (5.6 mg,
0.011 mmol), AgBF4 (2.5 mg, 0.013 mmol), and 2g (61.2 mg,
0.2 mmol) in dioxane (1 mL) at room temperature for 17 h afforded
3g (41.5 mg, 84%) after chromatography (petroleum ether/ethyl
acetate, 20:l) as a white solid; m.p. 97–98 °C (ethyl acetate/n-hex-
6-Iodo-1,4-dimethoxy-7-phenylnaphthalene (4a): A dried Schlenk
tube was charged with AuCl(PPh3) (8.0 mg, 0.016 mmol), AgBF4
(3.2 mg, 0.016 mmol), 2a (96.1 mg, 0.30 mmol), acetone (2 mL),
and NIS (100.1 mg, 0.44 mmol) sequentially at 0 °C under an at-
mosphere of N2. After stirring for 20 h, the reaction was complete
as monitored by TLC. The reaction mixture was diluted with di-
ethyl ether (10 mL) and quenched with saturated aqueous solution
of Na2S2O3. The mixture was extracted with diethyl ether
(3ϫ15 mL), and the combined organic layers were washed with
water and dried with anhydrous Na2SO4. Following filtration and
evaporation, the residue was purified by column chromatography
on silica gel (petroleum ether/ethyl acetate, 40:l) to afford 4a
(86.9 mg, 75%; 1H NMR yield by using CH2Br2 as the internal
1
ane). H NMR (300 MHz, CDCl3): δ = 7.68–7.60 (m, 2 H, ArH),
7.33 (dd, J = 8.4, 1.8 Hz, 1 H, ArH), 7.11 (s, 2 H, ArH), 6.05 (s, 2
H, OCH2O), 5.21 (s, 2 H, ArCH2O), 2.12 (s, 3 H, COCH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 170.9, 147.9, 131.8, 130.2, 127.3,
126.7, 124.5, 103.9, 103.7, 101.1, 66.5, 21.1 ppm. IR (KBr): ν =
˜
2955, 1737, 1467, 1380, 1365, 1253, 1173, 1149, 1076, 1034. MS
(70 eV, EI): m/z (%) = 245 (9.26) [M + 1]+, 244 (61.22) [M]+, 185
(100). C14H12O4 (244.25): calcd. C 68.85, H 4.95; found C 68.55,
H 4.98.
1
standard, 4a/3a = 100:0) as a liquid. H NMR (300 MHz, CDCl3):
δ = 8.89 (s, 1 H, ArH), 8.17 (s, 1 H, ArH), 7.52–7.40 (m, 5 H,
ArH), 6.74–6.68 (m, 2 H, ArH), 3.97 (s, 3 H, OCH3), 3.93 (s, 3 H,
OCH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.2, 148.1, 144.2,
143.1, 133.1, 129.6, 127.7, 127.5, 126.5, 125.6, 122.7, 104.0, 103.9,
1,2-Dimethoxy-6-phenylnaphthalene (3h): According to the general
procedure, the reaction of AuCl(PPh3) (7.5 mg, 0.015 mmol),
AgBF4 (3.5 mg, 0.018 mmol), and 2h (98.5 mg, 0.3 mmol) in diox-
ane (1.5 mL) at room temperature for 19 h afforded 3h (67.5 mg,
84%) after chromatography (petroleum ether/ethyl acetate, 10:l) as
a solid; m.p. 126–127 °C (ethyl acetate/n-hexane). 1H NMR
(300 MHz, CDCl3): δ = 7.91 (s, 1 H, ArH), 7.81–7.67 (m, 3 H,
ArH), 7.66–7.56 (m, 1 H, ArH), 7.48 (t, J = 7.5 Hz, 2 H, ArH),
7.36 (t, J = 7.5 Hz, 1 H, ArH), 7.19 (s, 1 H, ArH), 7.15 (s, 1 H,
ArH), 4.03 (s, 6 H, OCH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
149.7, 149.5, 141.3, 136.9, 129.4, 128.8, 128.3, 127.2, 127.0, 126.8,
96.8, 55.7, 55.6 ppm. IR (neat): ν = 3009, 2967, 2934, 2823, 1625,
˜
1579, 1498, 1459, 1413, 1395, 1322, 1274, 1237, 1212, 1155, 1107,
1089, 1020. MS (70 eV, EI): m/z (%) = 391 (21.10) [M + 1]+, 390
(100) [M]+. HRMS: calcd. for C18H15IO2 [M]+ 390.0117; found
390.0117.
(8-Iodonaphtho[2,1-d][1,3]dioxol-7-yl)methyl Acetate (4g): Accord-
ing to the procedure outlined for 4a, the reaction of AuCl(PPh3)
(7.4 mg, 0.015 mmol), AgBF4 (3.1 mg, 0.015 mmol), 2g (90.1 mg,
0.3 mmol), and NIS (105.1 mg, 0.47 mmol) in acetone (2 mL) at
124.3, 123.8, 106.5, 106.0, 55.9 ppm. IR (KBr): ν = 2967, 2931,
˜
2871, 1627, 1606, 1497, 1463, 1414, 1255, 1196, 1165, 1134, 1007.
MS (70 eV, EI): m/z (%) = 265 (18.89) [M + 1]+, 264 (100) [M]+.
C18H16O2 (264.32): calcd. C 81.79, H 6.10; found C 81.99, H 6.34.
1
0 °C for 11 h afforded 4g (65.4 mg, 60%; 62% H NMR yield by
using CH2Br2 as the internal standard, 4g/3g = 100:0) as a liquid.
6-Butyl-1,2,3-trimethoxynaphthalene (3i): According to the general
1H NMR (300 MHz, CDCl3): δ = 8.14 (s, 1 H, ArH), 7.62 (s, 1 H,
procedure, the reaction of AuCl(PPh3) (7.8 mg, 0.015 mmol), ArH), 7.04 (s, 1 H, ArH), 6.95 (s, 1 H, ArH), 6.05 (s, 2 H, OCH2O),
AgBF4 (3.5 mg, 0.018 mmol), and 2i (101.5 mg, 0.3 mmol) in diox-
ane (1.5 mL) at room temperature for 12 h afforded 3i (67.0 mg,
5.19 (s, 2 H, ArCH2O), 2.16 (s, 3 H, COCH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 170.6, 148.4, 148.3, 137.5, 132.9, 131.8,
80%) after chromatography (petroleum ether/ethyl acetate, 60:l) as
a liquid. H NMR (300 MHz, CDCl3): δ = 7.98 (d, J = 8.4 Hz, 1 = 2913, 1737, 1615, 1486, 1459, 1377, 1236, 1039. MS (70 eV, EI):
129.8, 127.8, 103.7, 102.4, 101.3, 93.1, 70.0, 21.0 ppm. IR (neat): ν
˜
1
H, ArH), 7.49 (s, 1 H, ArH), 7.23 (dd, J = 8.6, 1.7 Hz, 1 H, ArH),
m/z (%) = 370 (31.79) [M]+, 201 (100). HRMS: calcd. for
6.91 (s, 1 H, ArH), 4.06 (s, 3 H, OCH3), 3.981 (s, 3 H, OCH3), C14H11O4I [M]+ 369.9702; found 369.9708.
Eur. J. Org. Chem. 2010, 6545–6555
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6551

W. Kong, C. Fu, S. Ma
FULL PAPER
6-Butyl-7-iodo-1,2,3-trimethoxynaphthalene (4i): According to the
procedure outlined for 4a, the reaction of AuCl(PPh3) (7.4 mg,
(s, 3 H, OCH3), 3.92 (s, 3 H, OCH3), 2.92 (t, J = 7.8 Hz, 2 H), 2.04
(br. s, 1 H, OH), 1.80–1.65 (m, 2 H), 1.50–1.35 (m, 2 H), 0.97 (t, J
0.015 mmol), AgBF4 (3.5 mg, 0.015 mmol), 2i (101.5 mg, = 7.4 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.1,
0.3 mmol), and NIS (102.5 mg, 0.45 mmol) in acetone (2 mL) at 148.8, 141.3, 126.8, 125.8, 124.3, 120.7, 120.4, 104.2, 102.8, 90.2,
1
0 °C for afforded 4i (60.9 mg, 50%; 60% H NMR yield by using
CH2Br2 as the internal standard, 4i/3i = 100:0) as a liquid. 1H
NMR (300 MHz, CDCl3): δ = 8.52 (s, 1 H, ArH), 7.49 (s, 1 H,
ArH), 6.83 (s, 1 H, ArH), 4.04 (s, 3 H, OCH3), 3.96 (s, 3 H, OCH3),
3.95 (s, 3 H, OCH3), 2.81 (t, J = 7.8 Hz, 2 H), 1.71–1.58 (m, 2 H),
1.54–1.38 (m, 2 H), 0.98 (t, J = 7.4 Hz, 3 H, CH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 153.5, 146.6, 141.5, 140.4, 132.5, 130.5,
125.7, 124.3, 101.5, 96.2, 61.4, 61.1, 55.8, 40.3, 32.6, 22.4,
85.0, 55.6, 51.7, 34.4, 32.8, 22.5, 14.0 ppm. IR (neat): ν = 3384,
˜
2955, 2932, 2859, 1633, 1597, 1463, 1433, 1344, 1326, 1268, 1240,
1199, 1169, 1090, 1022. MS (70 eV, EI): m/z (%) = 298 (100) [M]+.
HRMS: calcd. for C19H22O3 [M]+ 298.1569; found 298.1569.
3-(7-Phenylnaphtho[2,1-d][1,3]dioxol-8-yl)prop-2-yn-1-ol (5c): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(5.1 mg, 0.01 mmol), AgBF4 (2.4 mg, 0.01 mmol), 2c (64.4 mg,
0.2 mmol), and NIS (66.8 mg, 0.3 mmol) in acetone (1 mL) at 0 °C
for 21 h afforded 4c in 77% 1H NMR yield by using CH2Br2 as the
internal standard (4c/3c = 94:6). Product 4c was then used without
further purification. The reaction of Pd(PPh3)2Cl2 (2.9 mg,
0.004 mmol), CuI (1.1 mg, 0.006 mmol), 4c (prepared in the pre-
vious step), DMSO (1 mL), prop-2-yn-1-ol (23.0 mg, 0.4 mmol),
and Et3N (1 mL) afforded 5c (38.7 mg, combined yield from 2c to
5c is 61%) after chromatography (petroleum ether/ethyl acetate, 5:1
to 2:1) as a solid; m.p. 143–144 °C (ethyl acetate/n-hexane). 1H
NMR (300 MHz, CDCl3): δ = 7.87 (s, 1 H, ArH), 7.65–7.60 (m, 3
H, ArH), 7.47–7.37 (m, 3 H, ArH), 7.07 (d, J = 8.4 Hz, 2 H, ArH),
5.99–6.11 (m, 2 H, OCH2O), 4.37 (d, J = 5.4 Hz, 2 H, HOCH2),
1.68 (br. s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.6,
148.1, 140.4, 139.2, 132.1, 130.4, 129.4, 129.1, 127.9, 127.5, 127.3,
14.0 ppm. IR (neat): ν = 2955, 2933, 2871, 1622, 1589, 1570, 1483,
˜
1459, 1424, 1393, 1368, 1241, 1205, 1151, 1110, 1042, 1002. MS
(70 eV, EI): m/z (%) = 400 (100) [M]+. HRMS: calcd. for C17H21O3I
[M]+ 400.0535; found 400.0530.
Synthesis of 3-(5,8-Dimethoxy-3-phenylnaphthalen-2-yl)prop-2-yn-1-
ol (5a) as a Representative General Procedure for the Preparation of
3-(Naphthalen-2-yl)prop-2-yn-1-ols by Gold-Catalyzed Cyclization
of 1-Arylalka-2,3-dienyl Acetates and Subsequent Sonogashira Cou-
pling Reaction with Propargyl Alcohol 2: The reaction of
AuCl(PPh3) (5.1 mg, 0.01 mmol), AgBF4 (2.5 mg, 0.01 mmol), 2a
(64.4 mg, 0.2 mmol), and NIS (67.9 mg, 0.3 mmol) in acetone
(1.5 mL) at 0 °C for 11 h afforded 4a in 84% 1H NMR yield by
using CH2Br2 as the internal standard (4a/3a = 100:0). Product 4a
was then used without further purification. A Schlenk tube was
charged with Pd(PPh3)2Cl2 (2.9 mg, 0.004 mmol), CuI (1.2 mg,
0.006 mmol), 4a (prepared in the previous step), Et3N (1 mL),
prop-2-yn-1-ol (25.1 mg, 0.45 mmol), and DMSO (1 mL) sequen-
tially. The mixture was heated at 40 °C under an atmosphere of
nitrogen. After the reaction was complete as monitored by TLC,
the reaction was quenched with water (5 mL). The aqueous layer
was extracted with diethyl ether (3ϫ15 mL), and the combined
organic layers were washed with water and dried with anhydrous
Na2SO4. Following filtration and evaporation, the residue was puri-
fied by column chromatography on silica gel (petroleum ether/ethyl
acetate, 5:1) to afford 5a (36.9 mg, combined yield from 2a to 5a
is 58%) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 8.47 (s, 1 H,
ArH), 8.20 (s, 1 H, ArH), 7.75–7.65 (m, 2 H, ArH), 7.51–7.34 (m,
3 H, ArH), 6.72 (d, J = 8.4 Hz, 1 H, ArH), 6.69 (d, J = 8.4 Hz, 1
H, ArH), 4.38 (s, 2 H, CH2OH), 3.96 (s, 3 H, OCH3), 3.94 (s, 3 H,
OCH3), 1.76 (br. s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ
= 149.3, 148.9, 140.6, 140.3, 129.5, 127.8, 127.6, 127.3, 125.7, 124.8,
122.5, 118.9, 104.6, 103.8, 90.1, 85.9, 55.71, 55.66, 51.7 ppm. IR
117.4, 103.8, 103.2, 101.2, 89.7, 85.7, 51.7 ppm. IR (KBr): ν = 3327,
˜
2204, 1483, 1460, 1444, 1275, 1227, 1158, 1038, 1023. MS (70 eV,
EI): m/z (%) = 302 (100) [M]+. C20H14O3 (302.33): calcd. C 79.46,
H 4.67; found C 79.42, H 4.74.
3-(7-Butylnaphtho[2,1-d][1,3]dioxol-8-yl)prop-2-yn-1-ol (5d): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(7.4 mg, 0.015 mmol), AgBF4 (3.5 mg, 0.015 mmol), 2d (87.0 mg,
0.3 mmol), and NIS (101.2 mg, 0.45 mmol) in acetone (2 mL) at
1
0 °C for 12 h afforded 4d in 89% H NMR yield by using CH2Br2
as the internal standard (4d/3d = 95:5). Product 4d was then used
without further purification. The reaction of Pd(PPh3)2Cl2 (4.3 mg,
0.006 mmol), CuI (1.4 mg, 0.007 mmol), 4d (prepared in the pre-
vious step), DMSO (1 mL), prop-2-yn-1-ol (34.1 mg, 0.6 mmol),
and Et3N (1 mL) afforded 5d (56.8 mg, combined yield from 2d to
5d is 67%) after chromatography (petroleum ether/ethyl acetate,
1
10:1 to 5:1) as a solid; m.p. 98–99 °C (ethyl acetate/n-hexane). H
NMR (300 MHz, CDCl3): δ = 7.73 (s, 1 H, ArH), 7.40 (s, 1 H,
ArH), 7.00 (s, 1 H, ArH), 6.98 (s, 1 H, ArH), 6.00 (s, 2 H, OCH2O),
4.57 (s, 2 H, HOCH2), 2.83 (t, J = 7.8 Hz, 2 H), 2.10 (br. s, 1 H,
OH), 1.75–1.59 (m, 2 H), 1.50–1.31 (m, 2 H), 0.96 (t, J = 7.4 Hz,
3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.2, 147.3,
139.8, 131.3, 130.5, 128.2, 126.1, 118.8, 103.3, 103.2, 101.0, 89.9,
(neat): ν = 3385, 3000, 2936, 2833, 2252, 2216, 1626, 1592, 1499,
˜
1460, 1431, 1393, 1333, 1277, 1266, 1213, 1157, 1101, 1038, 1024.
MS (70 eV, EI): m/z (%) = 319 (23.48) [M + 1]+, 318 (100) [M]+.
HRMS: calcd. for C21H18O3 [M]+ 318.1256; found 318.1257.
84.8, 51.7, 34.0, 32.7, 22.5, 14.0 ppm. IR (KBr): ν = 3331, 2961,
˜
3-(3-Butyl-5,8-dimethoxynaphthalen-2-yl)prop-2-yn-1-ol (5b): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(7.3 mg, 0.015 mmol), AgBF4 (3.1 mg, 0.015 mmol), 2b (91.2 mg,
0.3 mmol), and NIS (100.9 mg, 0.45 mmol) in acetone (2 mL) at
2928, 2847, 1633, 1613, 1491, 1461, 1441, 1353, 1257, 1230, 1211,
1155, 1040. MS (70 eV, EI): m/z (%) = 282 (100) [M]+. C18H18O3
(282.34): calcd. C 76.57, H 6.43; found C 76.55, H 6.32.
1
0 °C for 12 h afforded 4b in 79% H NMR yield by using CH2Br2
3-(7-p-Tolylnaphtho[2,1-d][1,3]dioxol-8-yl)prop-2-yn-1-ol (5e): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(7.3 mg, 0.015 mmol), AgBF4 (3.1 mg, 0.015 mmol), 2e (96.6 mg,
0.3 mmol), and NIS (102.4 mg, 0.45 mmol) in acetone (2 mL) at
as the internal standard (4b/3b = 94:6). After column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate, 40:1), the mixture
was used in next step. The reaction of Pd(PPh3)2Cl2 (4.4 mg,
0.006 mmol), CuI (2.1 mg, 0.011 mmol), 4b (prepared in the pre-
vious step), DMSO (1 mL), prop-2-yn-1-ol (35.6 mg, 0.64 mmol),
and Et3N (1 mL) afforded 5b (47.7 mg, combined yield from 2b to
1
0 °C for 16 h afforded 4e in 89% H NMR yield by using CH2Br2
as the internal standard (4e/3e = 95:5). After column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate, 40:1), the mixture
5b is 53%) after chromatography (petroleum ether/ethyl acetate, was used in next step. The reaction of Pd(PPh3)2Cl2 (4.5 mg,
7:1) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 8.33 (s, 1 H,
ArH), 7.99 (d, J = 0.3 Hz, 1 H, ArH), 6.65 (d, J = 8.4 Hz, 1 H,
0.006 mmol), CuI (2.0 mg, 0.011 mmol), 4e (prepared in the pre-
vious step), DMSO (1 mL), prop-2-yn-1-ol (40.0 mg, 0.71 mmol),
ArH), 6.61 (d, J = 8.4 Hz, 1 H, ArH), 4.57 (s, 2 H, HOCH2), 3.94 and Et3N (1 mL) afforded 5e (49.5 mg, combined yield from 2e to
6552
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 6545–6555

Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
5e is 52%) as a solid; m.p. 166–167 °C (ethyl acetate/n-hexane). 1H
vious step), DMSO (1.5 mL), prop-2-yn-1-ol (35.2 mg, 0.6 mmol),
NMR (300 MHz, CDCl3): δ = 7.86 (s, 1 H, ArH), 7.60 (s, 1 H, and Et3N (1.5 mL) afforded 5h (41.2 mg, combined yield from 2h
ArH), 7.53 (d, J = 7.8 Hz, 2 H, ArH), 7.24 (d, J = 7.2 Hz, 2 H,
ArH), 7.06 (d, J = 6.9 Hz, 2 H, ArH), 6.04 (s, 2 H, OCH2O), 4.38
to 5h is 43%) after chromatography (petroleum ether/ethyl acetate,
3:1) as a liquid. 1H NMR (300 MHz, CDCl3): δ = 7.92 (s, 1 H,
(s, 2 H, HOCH2), 2.41 (s, 3 H, ArCH3), 1.65–1.45 (m, 1 H, ArH), 7.80–7.58 (m, 3 H, ArH), 7.57–7.28 (m, 3 H, ArH), 7.08 (d,
OH) ppm. 13C NMR (75 MHz, CDCl3): δ = 148.6, 148.1, 139.2, J = 8.7 Hz, 2 H, ArH), 4.39 (d, J = 5.7 Hz, 2 H, HOCH2), 4.01 (s,
137.5, 137.1, 132.1, 130.5, 129.2, 128.9, 128.6, 127.4, 117.4, 103.8,
6 H, OCH3), 1.62–1.44 (m, 1 H, OH) ppm. 13C NMR (75 MHz,
CDCl3): δ = 150.5, 150.0, 140.6, 139.1, 131.5, 129.5, 129.1, 127.9,
127.8, 127.3, 126.9, 117.2, 106.2, 105.6, 89.6, 85.9, 55.9, 51.8 ppm.
103.2, 101.2, 89.7, 85.9, 51.8, 21.2. IR (KBr): ν = 3382, 3009, 2905,
˜
2233, 1612, 1485, 1458, 1438, 1384, 1342, 1278, 1226, 1183, 1158,
1115, 1088, 1035, 1000. MS (70 eV, EI): m/z (%) = 316 (100) [M]+.
C21H16O3 (316.36): calcd. C 79.73, H 5.10; found C 79.74, H 5.37.
IR (neat): ν = 3429, 2937, 2859, 2240, 1621, 1600, 1497, 1420, 1356,
˜
1275, 1241, 1149, 1007. MS (70 eV, EI): m/z (%) = 300 (19.20) [M –
H2O]+, 284 (100). HRMS: calcd. for C21H18O3 [M]+ 318.1256;
found 318.1251.
3-{7-(Ethoxymethyl)naphtho[2,1-d][1,3]dioxol-8-yl}prop-2-yn-1-ol (5f):
According to the general procedure, the reaction of AuCl(PPh3)
(7.9 mg, 0.016 mmol), AgBF4 (4.2 mg, 0.022 mmol), 2f (87.1 mg,
0.3 mmol), and NIS (102.5 mg, 0.45 mmol) in acetone (2 mL) at
3-(3-Butyl-6,7,8-trimethoxynaphthalen-2-yl)prop-2-yn-1-ol (5i): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(7.5 mg, 0.015 mmol), AgBF4 (3.2 mg, 0.015 mmol), 2i (101.5 mg,
0.3 mmol), and NIS (101.5 mg, 0.45 mmol) in acetone (2 mL) at
1
0 °C for 14 h afforded 4f in 71% H NMR yield by using CH2Br2
as the internal standard (4f/3f = 96:4). After column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate, 40:1), the mixture
was used in next step. The reaction of Pd(PPh3)2Cl2 (4.3 mg,
0.006 mmol), CuI (1.9 mg, 0.010 mmol), 4f (prepared in the pre-
vious step), DMSO (1.5 mL), prop-2-yn-1-ol (34.1 mg, 0.6 mmol),
and Et3N (1.5 mL) afforded 5f (47 mg, combined yield from 2f to
1
0 °C for 11 h afforded 4i in 62% H NMR yield by using CH2Br2
as the internal standard (4i/3i = 100:0). Product 4i was then used
without further purification. The reaction of Pd(PPh3)2Cl2 (4.4 mg,
0.006 mmol), CuI (1.2 mg, 0.006 mmol), 4i (prepared in the pre-
vious step), DMSO (1.5 mL), prop-2-yn-1-ol (35.1 mg, 0.6 mmol),
and Et3N (1.5 mL) afforded 5i (47.5 mg, combined yield from 2i to
1
5f is 47%) as a liquid. H NMR (300 MHz, CDCl3): δ = 7.72 (s, 1
1
H, ArH), 7.66 (s, 1 H, ArH), 7.06 (s, 1 H, ArH), 6.99 (s, 1 H, ArH),
6.02 (s, 2 H, OCH2O), 4.73 (d, J = 0.6 Hz, 2 H, HOCH2), 4.53 (s,
2 H, CH2OEt), 3.63 (q, J = 7.0 Hz, 2 H), 2.85–2.72 (br. s, 1 H,
5i is 48%) as a liquid. H NMR (300 MHz, CDCl3): δ = 8.14 (s, 1
H, ArH), 7.44 (s, 1 H, ArH), 6.84 (s, 1 H, ArH), 4.57 (d, J =
2.1 Hz, 2 H, HOCH2), 4.03 (s, 3 H, OCH3), 3.95 (s, 6 H, OCH3),
OH), 1.30 (t, J = 6.9 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, 2.85 (t, J = 7.8 Hz, 2 H), 2.13 (br. s, 1 H, OH), 1.74–1.60 (m, 2 H),
CDCl3): δ = 148.3, 147.9, 135.0, 131.3, 130.2, 129.2, 125.7, 117.5,
103.8, 103.3, 101.1, 91.0, 83.5, 70.8, 66.0, 51.5, 15.2 ppm. IR (neat):
1.48–1.32 (m, 2 H), 0.95 (t, J = 7.2 Hz, 3 H, CH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 153.7, 147.4, 141.1, 140.4, 130.7, 126.5,
125.4, 122.3, 118.2, 101.7, 89.7, 85.0, 61.4, 61.1, 55.8, 51.7, 34.0,
ν = 3386, 2991, 2903, 2865, 2222, 1609, 1495, 1462, 1371, 1359,
˜
1256, 1223, 1101, 1038. MS (70 eV, EI): m/z (%) = 284 (100) [M]+.
32.7, 22.4, 13.9 ppm. IR (neat): ν = 3391, 2924, 1728, 1699, 1492,
˜
HRMS: calcd. for C17H16O4 [M]+ 284.1049; found 284.1057.
1453, 1434, 1380, 1261, 1230, 1086, 1026. MS (70 eV, EI): m/z (%)
= 329 (22.18) [M + 1]+, 328 (100). HRMS: calcd. for C20H24O4
[M]+ 328.1675; found 328.1682.
{8-(3-Hydroxyprop-1-ynyl)naphtho[2,1-d][1,3]dioxol-7-yl}methyl
Acetate (5g): According to the general procedure, the reaction of
AuCl(PPh3) (5.1 mg, 0.01 mmol), AgBF4 (2.2 mg, 0.01 mmol), 2g Synthesis of 1,4-Dimethoxy-6,7-diphenylnaphthalene (6a) as a Rep-
(60.5 mg, 0.2 mmol), and NIS (68.2 mg, 0.3 mmol) in acetone
(1.5 mL) at 0 °C for 11 h afforded 4g in 62% 1H NMR yield by
using CH2Br2 as the internal standard (4g/3g = 100:0). Product 4g
was then used without further purification. The reaction of
resentative General Procedure for the Suzuki Coupling Reactions:[23]
Schlenk tube was charged with Pd(PPh3)4 (8.9 mg,
0.0077 mmol), TBAB (2.5 mg, 0.0075 mmol), K2CO3 (42.0 mg,
A
0.30 mmol), H2O (0.15 mL), PhB(OH)2 (25.1 mg, 0.21 mmol), 4a
Pd(PPh3)2Cl2 (2.9 mg, 0.004 mmol), CuI (1.2 mg, 0.006 mmol), 4g (57.0 mg, 0.15 mmol), and THF (1.5 mL) sequentially. The mixture
(prepared in the previous step), DMSO (1 mL), prop-2-yn-1-ol
(23.9 mg, 0.4 mmol), and Et3N (1 mL) afforded 5g (28.6 mg, com-
bined yield from 2g to 5g is 48%) after chromatography (petroleum
ether/ethyl acetate, 5:1 to 1:1) as a liquid. 1H NMR (300 MHz,
CDCl3): δ = 7.75 (s, 1 H, ArH), 7.61 (s, 1 H, ArH), 7.05 (s, 1 H,
ArH), 7.01 (s, 1 H, ArH), 6.05 (s, 2 H, OCH2O), 5.35 (s, 2 H,
was heated at reflux under an atmosphere of nitrogen. After the
reaction was complete as monitored by TLC, evaporation of the
solvents and purification by column chromatography on silica gel
(petroleum ether/ethyl acetate, 20:l) afforded 6a (39.8 mg, 80%) as
1
a white solid; m.p. 171–172 °C (ethyl acetate/n-hexane). H NMR
(300 MHz, CDCl3): δ = 8.26 (s, 2 H, ArH), 7.30–7.15 (m, 10 H,
HOCH2), 4.52 (d, J = 5.4 Hz, 2 H, CH2OAc), 2.45 (br. s, 1 H, ArH), 6.72 (s, 2 H, ArH), 3.97 (s, 6 H, OCH3) ppm. 13C NMR
OH), 2.14 (s, 3 H, COCH3) ppm. 13C NMR (75 MHz, CDCl3): δ
(75 MHz, CDCl3): δ = 149.6, 141.8, 138.9, 130.1, 127.7, 126.4,
= 171.3, 148.6, 148.4, 132.5, 131.3, 130.0, 129.8, 127.3, 118.0, 103.9,
125.6, 123.7, 103.6, 55.8 ppm. IR (KBr): ν = 2991, 2934, 2831,
˜
103.4, 101.3, 91.4, 83.2, 64.9, 51.5, 21.1 ppm. IR (neat): ν = 3445,
1625, 1579, 1498, 1459, 1413, 1322, 1274, 1237, 1107, 1091. MS
(70 eV, EI): m/z (%) = 341 (26.01) [M + 1]+, 340 (100) [M]+.
C24H20O2 (340.42): calcd. C 84.68, H 5.92; found C 84.41, H 6.02.
˜
2933, 2859, 2225, 1626, 1602, 1567, 1489, 1467, 1427, 1398, 1300,
1267, 1226, 1203, 1154, 1102, 1036, 1001. MS (70 eV, EI): m/z (%)
= 298 (100) [M]+, 238 (85.62) [M – HOAc]+. HRMS: calcd. for
C17H14O5 [M]+ 298.0841; found 298.0847.
1,4-Dimethoxy-6-(4-methoxyphenyl)-7-phenylnaphthalene (7a): Ac-
cording to the general procedure, the reaction of Pd(PPh3)4
(12.1 mg, 0.01 mmol), TBAB (3.3 mg, 0.01 mmol), K2CO3
(56.1 mg, 0.40 mmol), H2O (0.20 mL), 4-methoxyphenylboronic
3-(7,8-Dimethoxy-3-phenylnaphthalen-2-yl)prop-2-yn-1-ol (5h): Ac-
cording to the general procedure, the reaction of AuCl(PPh3)
(7.5 mg, 0.015 mmol), AgBF4 (3.5 mg, 0.015 mmol), 2h (97.1 mg, acid (34.0 mg, 0.22 mmol), 4a (78.5 mg, 0.20 mmol), and THF
0.3 mmol), and NIS (101.1 mg, 0.45 mmol) in acetone (2 mL) at
0 °C for 12 h afforded 4h in 71% H NMR yield by using CH2Br2
as the internal standard (4h/3h = 91:9). Product 4h was then used
without further purification. The reaction of Pd(PPh3)2Cl2 (4.3 mg,
0.006 mmol), CuI (2.0 mg, 0.010 mmol), 4h (prepared in the pre-
(2 mL) afforded 7a (63.3 mg, 85%) after chromatography (petro-
leum ether/ethyl acetate, 80:1) as a liquid. 1H NMR (300 MHz,
CDCl3): δ = 8.23 (d, J = 1.5 Hz, 2 H, ArH), 7.30–7.10 (m, 5 H,
ArH), 7.16 (d, J = 8.7 Hz, 2 H, ArH), 6.77 (d, J = 8.7 Hz, 2 H,
ArH), 6.69 (s, 2 H, ArH), 3.944 (s, 3 H, OCH3), 3.939 (s, 3 H,
1
Eur. J. Org. Chem. 2010, 6545–6555
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6553

W. Kong, C. Fu, S. Ma
FULL PAPER
OCH3), 3.76 (s, 3 H, OCH3) ppm. 13C NMR (75 MHz, CDCl3): δ
= 158.3, 149.5, 149.4, 141.9, 138.9, 138.5, 134.1, 131.1, 130.0, 127.8,
126.3, 125.6, 125.3, 123.7, 123.4, 113.2, 103.5, 103.4, 55.7,
1293–1305; e) X. Xie, M. C. Kozlowski, Org. Lett. 2001, 3,
2661–2663.
M. D. Watson, A. Fechtenkötter, K. Müllen, Chem. Rev. 2001,
101, 1267–1300.
C. B. Koning, A. L. Rousseau, W. A. L. Otterlo, Tetrahedron
2003, 59, 7–36.
a) J. March, Advanced Organic Chemistry, 4th ed., Wiley, New
York, 1992, ch. 11, p. 501; b) R. Norman, J. M. Coxon, Prin-
ciples of Organic Synthesis, 3rd ed., Chapman & Hall, New
York, 1993, p. 355.
a) M. L. N. Rao, O. Yamozaki, S. Shimada, T. Tanaka, Y. Su-
zuki, M. Tanaka, Org. Lett. 2001, 3, 4103–4105; b) D. Zim,
V. R. Lando, J. Dupont, A. L. Monteiro, Org. Lett. 2001, 3,
3049–3051; c) D. D. Hennings, T. Iwama, V. H. Rawel, Org.
Lett. 1999, 1, 1205–1208.
a) T. Kamikawa, T. Hayashi, Tetrahedron Lett. 1997, 38, 7087–
7090; b) R. E. Merrill, E. Negishi, J. Org. Chem. 1974, 39,
3452–3453.
[2]
[3]
[4]
55.1 ppm. IR (neat): ν = 2999, 2934, 2834, 1609, 1594, 1515, 1460,
˜
1432, 1333, 1271, 1247, 1224, 1178, 1105, 1048, 1034. MS (70 eV,
EI): m/z (%) = 371 (26.90) [M + 1]+, 370 (100) [M]+. HRMS: calcd.
for C25H22O3 [M]+ 370.1569; found 370.1566.
(E)-1,4-Dimethoxy-6-phenyl-7-styrylnaphthalene (8a): According to
the general procedure, the reaction of Pd(PPh3)4 (12.5 mg,
0.01 mmol), TBAB (3.5 mg, 0.01 mmol), K2CO3 (59.2 mg,
0.40 mmol), H2O (0.20 mL), (E)-styrylboronic acid (35.1 mg,
0.22 mmol), 4a (74.1 mg, 0.19 mmol), and THF (2 mL) afforded 8a
(50.5 mg, 73%) after chromatography (petroleum ether/ethyl acet-
[5]
[6]
1
ate, 200:1) as a liquid. H NMR (300 MHz, CDCl3): δ = 8.57 (s, 1
H, CH=CH), 8.16 (s, 1 H, CH=CH), 7.54–7.38 (m, 7 H, ArH),
7.31 (t, J = 7.5 Hz, 2 H, ArH), 7.26–7.18 (m, 3 H, ArH), 6.72 (d,
J = 8.4 Hz, 1 H, ArH), 6.69 (d, J = 8.4 Hz, 1 H, ArH), 4.02 (s, 3 [7]
H, OCH3), 3.95 (s, 3 H, OCH3) ppm. 13C NMR (75 MHz, CDCl3): [8]
δ = 149.53, 149.49, 141.1, 139.4, 137.7, 134.0, 130.1, 129.9, 128.6,
128.2, 128.0, 127.4, 127.0, 126.6, 125.7, 125.5, 123.2, 118.9, 103.5,
C. K. Bradsher, Chem. Rev. 1987, 87, 1277–1297.
a) P. Turnbull, H. W. Moore, J. Org. Chem. 1995, 60, 644–649;
b) R. Tiedemann, P. Turnbull, H. W. Moore, J. Org. Chem.
1999, 64, 4030–4041; c) D. J. Chang, B. S. Park, Tetrahedron
Lett. 2001, 42, 711–713; d) K. Wakasugi, Y. Nishii, Y. Tanabe,
Tetrahedron Lett. 2000, 41, 5937–5942; e) T. Matsumoto, T.
Hamura, M. Miyamoto, K. Suzuki, Tetrahedron Lett. 1998, 39,
4853–4856.
a) G. Wu, A. L. Rheingold, S. J. Geib, R. F. Heck, Organome-
tallics 1987, 6, 1941–1946; b) G. Wu, A. L. Rheingold, R. F.
Heck, Organometallics 1986, 5, 1922–1924; c) T. Takahashi, Y.
Li, P. Slepnicka, M. Kitamura, Y. Liu, K. Nakajima, M. Ko-
tora, J. Am. Chem. Soc. 2002, 124, 576–582; d) R. C. Larock,
Q. Tian, J. Org. Chem. 1998, 63, 2002–2009; e) R. C. Larock,
M. J. Doty, Q. Tian, J. M. Zenner, J. Org. Chem. 1997, 62,
7536–7537; f) T. Fukutani, K. Hirano, T. Satoh, M. Miura,
Org. Lett. 2009, 11, 5198–5201; g) Q. Huang, R. C. Larock,
Org. Lett. 2002, 4, 2505–2508.
a) E. Yoshikawa, Y. Yamamoto, Angew. Chem. Int. Ed. 2000,
39, 173–175; b) K. V. Radhakrishnan, E. Yoshikawa, Y. Yama-
moto, Tetrahedron Lett. 1999, 40, 7533–7535; c) E. Yoshikawa,
K. V. Radhakrishnan, Y. Yamamoto, J. Am. Chem. Soc. 2000,
122, 7280–7286; d) D. Peña, D. Pérez, E. Guitián, L. Castedo,
J. Am. Chem. Soc. 1999, 121, 5827–5828; e) J.-C. Hsieh, C.-H.
Cheng, Chem. Commun. 2005, 2459–2461.
a) R. C. Larock, M. J. Doty, Q. Tian, J. M. Zenner, J. Org.
Chem. 1997, 62, 7536–7537; b) R. C. Larock, Q. Tian, J. Org.
Chem. 1998, 63, 2002–2009; c) R. C. Larock, J. Organomet.
Chem. 1999, 576, 111–124.
103.4, 55.8, 55.7 ppm. IR (neat): ν = 2943, 1593, 1492, 1461, 1435,
˜
1326, 1269, 1241, 1143, 1094. MS (70 eV, EI): m/z (%) = 367 (31.96)
[M + 1]+, 366 (100) [M]+. HRMS: calcd. for C26H22O2 [M]+
366.1620; found 366.1619.
[9]
Synthesis of 1,4-Dimethoxy-6-[(4-methoxyphenyl)ethynyl]-7-phenyl-
naphthalene (9a) Following the Procedure for the Sonogashira Cou-
pling:[23] The reaction of Pd(PPh3)2Cl2 (3.5 mg, 0.005 mmol), CuI
(1.9 mg, 0.01 mmol), 4a (78.0 mg, 0.20 mmol), Et3N (1 mL), 1-eth-
ynyl-4-methoxybenzene (35.1 mg, 0.27 mmol), and DMSO (1 mL)
afforded 9a (72.1 mg, 91%) after chromatography (petroleum ether/
1
ethyl acetate, 30:1) as a liquid. H NMR (300 MHz, CDCl3): δ =
8.55 (d, J = 0.3 Hz, 1 H, ArH), 8.27 (d, J = 0.6 Hz, 1 H, ArH),
7.88–7.78 (m, 2 H, ArH), 7.58–7.40 (m, 3 H, ArH), 7.38–7.28 (m,
2 H, ArH), 6.90–6.80 (m, 2 H, ArH), 6.71 (s, 2 H, ArH), 3.99 (s, 3
H, OCH3), 3.95 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 159.4, 149.5, 149.0, 140.9, 140.4,
132.8, 129.7, 127.7, 127.3, 126.7, 125.5, 125.0, 122.4, 120.1, 115.7,
[10]
113.9, 104.3, 103.8, 92.5, 88.8, 55.8, 55.7, 55.3 ppm. IR (neat): ν =
˜
3000, 2934, 2835, 2205, 1625, 1605, 1591, 1512, 1462, 1432, 1393,
1335, 1273, 1248, 1235, 1173, 1135, 1091, 1033. MS (70 eV, EI):
m/z (%) = 395 (29.55) [M + 1]+, 394 (100) [M]+. HRMS: calcd. for
C27H22O3 [M]+ 394.1569; found 394.1564.
[11]
[12]
a) N. E. Shore, Chem. Rev. 1988, 88, 1081–1119; b) K. H. Dötz,
Angew. Chem. Int. Ed. Engl. 1984, 23, 587–608; c) S. Duan,
D. K. Sinha-Mahapatra, J. W. Herndon, Org. Lett. 2008, 10,
1541–1544.
Supporting Information (see footnote on the first page of this arti-
cle): Detailed experimental procedures, analytical data, and copies
1
of the H and 13C NMR spectra of all compounds.
[13]
[14]
a) G. S. Viswanathan, M. Wang, C.-J. Li, Angew. Chem. Int.
Ed. 2002, 41, 2138–2141; b) G. W. Kabalka, Y. Ju, Z. Wu, J.
Org. Chem. 2003, 68, 7915–7917.
a) J. Barluenga, E. Campos-Gómez, A. Minatti, D. Rodríguez,
J. M. González, Chem. Eur. J. 2009, 15, 8946–8950; b) G. Chai,
Z. Lu, C. Fu, S. Ma, Chem. Eur. J. 2009, 15, 11083–11086; c)
Y. Kuninobu, Y. Nishina, T. Takai, Tetrahedron 2007, 63, 8463–
8468; d) H. Kusama, H. Funami, N. Iwasawa, Synthesis 2007,
2014–2024.
W. Kong, C. Fu, S. Ma, Chem. Commun. 2009, 4572–4574.
For a report involving the enantioselective intramolecular hy-
drarylation with indoles, see: C. Liu, A. Widenhofer, Org. Lett.
2007, 9, 1935–1938.
Acknowledgments
Financial support from the Major State Basic Research and Devel-
opment Program (2009CB825300) and the National Natural Sci-
ence Foundation of China (20732005) is greatly appreciated. S.M.
is a Qiu Shi Adjunct Professor at Zhejiang University. We thank
Mr. Pengbin Li in this group for reproducing the results presented
in Table 2 (Entries 1, 6, and 10) and for repreparing compound 8a
in Scheme 8.
[15]
[16]
[17]
[18]
C. Park, P. H. Lee, Org. Lett. 2008, 10, 3359–3362.
T. Watanabe, S. Ohishi, N. Fujii, H. Ohno, Org. Lett. 2007, 9,
4821–4824.
M. A. Tarselli, M. R. Gagné, J. Org. Chem. 2008, 73, 2439–
2441.
[1] a) B. L. Seong, M. H. Han, Chem. Lett. 1982, 627–628; b) J. M.
Trujillo, R. E. Jorge, E. Navarro, J. Boada, Phytochemistry
1990, 29, 2991–2993; c) R. S. Ward, Nat. Prod. Rep. 1995, 12,
183–205; d) T. Ukita, Y. Nakamura, A. Kubo, Y. Yamamoto,
M. Takahashi, J. Kotera, T. Ikeo, J. Med. Chem. 1999, 42,
[19]
6554
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Eur. J. Org. Chem. 2010, 6545–6555

Gold-Catalyzed Cyclization of 1-Arylalka-2,3-dienyl Acetates
[20] a) A. Hoffmann-Röder, N. Krause, Org. Lett. 2001, 3, 2537–
2538; b) A. Hoffmann-Röder, N. Krause, Org. Biomol. Chem.
2005, 3, 387–391; c) B. Gockel, N. Krause, Org. Lett. 2006, 8,
4485–4488; d) A. S. K. Hashmi, M. C. Blanco, D. Fischer, J. W.
Bats, Eur. J. Org. Chem. 2006, 1387–1389; e) C. J. T. Hyland,
L. S. Hegedus, J. Org. Chem. 2006, 71, 8658–8660; f) A. S. K.
Hashmi, Chem. Rev. 2007, 107, 3180–3211; g) R. W. Bates, V.
Satcharoen, Chem. Soc. Rev. 2002, 31, 12–21; h) M. P. Van-
brunt, R. F. Standaert, Org. Lett. 2000, 2, 705–708; i) A.
Fürstner, E. Kattnig, O. Lepage, J. Am. Chem. Soc. 2006, 128,
9194–9204; j) O. Lepage, E. Kattnig, A. Fürstner, J. Am. Chem.
Soc. 2004, 126, 15970–15971; k) J. A. Marshall, R. H. Yu, J. F.
Perkins, J. Org. Chem. 1995, 60, 5550–5555; l) N. Krause,
A. S. K. Hashmi (Eds.), Modern Allene Chemistry, Wiley-VCH,
Weinheim, Germany, 2004, vols. 1 and 2.
Y. Wang, W. A. Goddard III, F. D. Toste, Nat. Chem. 2009,
482–486.
[22] a) M. Yu, G. Zhang, L. Zhang, Org. Lett. 2007, 9, 2147–2150;
b) L. Ye, G. Zhang, L. Zhang, Org. Lett. 2009, 11, 3646–3649;
c) A. Buzas, F. Gagosz, Org. Lett. 2006, 8, 515–518; d) A.
Buzas, F. Istrate, F. Gagosz, Org. Lett. 2006, 8, 1957–1959; e)
S. F. Kirsch, J. T. Binder, B. Crone, A. Duschek, T. T. Haug, C.
Liébert, H. Menz, Angew. Chem. Int. Ed. 2007, 46, 2310–2313.
[23] S. Ma, H. Ren, Q. Wei, J. Am. Chem. Soc. 2003, 125, 4817–
4830.
[24] a) B. Alcaide, P. Almendros, C. Aragoncillo, M. C. Redondo,
Eur. J. Org. Chem. 2005, 98–106; b) T. Mukaiyama, T. Harada,
Chem. Lett. 1981, 621–624; c) J. Li, W. Kong, C. Fu, S. Ma, J.
Org. Chem. 2009, 74, 5104–5106; d) P. Place, C. Verniere, J.
Gore, Tetrahedron 1981, 37, 1359–1367; e) W. Kong, C. Fu, S.
Ma, Org. Biomol. Chem. 2008, 6, 4587–4592; f) Y. Deng, X.
Jin, S. Ma, J. Org. Chem. 2007, 72, 5901–5904.
[21] a) A. Fürstner, L. Morency, Angew. Chem. Int. Ed. 2008, 47,
5030–5033; b) G. Seidel, R. Mynott, A. Fürstner, Angew.
Chem. Int. Ed. 2009, 48, 2510–2513; c) B. P. Taduri, S. Md, A.
Sohel, H.-M. Cheng, G.-Y. Lin, R.-S. Liu, Chem. Commun.
2007, 2530–2532; d) D. Benitez, N. D. Shapiro, E. Tkatchouk,
Received: August 7, 2010
Published Online: October 4, 2010
Eur. J. Org. Chem. 2010, 6545–6555
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6555