Domino hydroarylation-cyclization reaction: One-pot synthesis of indane-fused 3,4-dihydrocoumarins

Article abstract of DOI:10.1002/adsc.201200745

A tin(II) triflate-catalyzed domino hydroarylation-cyclization reaction has been developed to access a wide-variety of methyleneindane-fused 3,4-hydrocoumarins. A judiciously selected bi-functional Lewis acidic catalyst has been successfully applied to promote two ring-closing events as a single-pot operation.

Full text of DOI:10.1002/adsc.201200745

FULL PAPERS
DOI: 10.1002/adsc.201200745
Domino Hydroarylation–Cyclization Reaction: One-Pot Synthesis
of Indane-Fused 3,4-Dihydrocoumarins
Jin Hyuck Jooa and So Won Youna,*
a
Department of Chemistry and Research Institute for Natural Sciences, Hanyang University, Seoul 133-791, Korea
Fax : (+82)-2-2299-0762; e-mail: sowony73@hanyang.ac.kr
Received: August 20, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200745.
Abstract: A tin(II) triflate-catalyzed domino hydro- promote two ring-closing events as a single-pot oper-
arylation–cyclization reaction has been developed to ation.
access a wide-variety of methyleneindane-fused 3,4-
hydrocoumarins. A judiciously selected bi-functional Keywords: cyclization; domino reactions; fused-ring
Lewis acidic catalyst has been successfully applied to systems; hydroarylation; tin
Introduction
Results and Discussion
Domino reactions are powerful synthetic transforma- On close examination of the proposed domino reac-
tions that render a high degree of molecular complex- tion (Scheme 1a), the rationale for our synthetic
ity from structurally simplified and easily accessible design rests its foundation on two well-documented
progenitor(s) in a highly efficient manner.[1] In partic- constituting chemical processes. First, Lewis/Brønsted
ular, substrates bearing judiciously positioned carbon- acid-catalyzed hydroarylation of cinnamic acid deriva-
carbon multiple bonds could be programmed to un- tives with phenols is a reported method for the prepa-
dergo sequential C C and/or C X (X=heteroatom) ration of 3,4-dihydrocoumarins.[7] On the other hand,
bond constructions, thereby furnishing a diverse array sequential conjugate addition–cyclization reactions of
of (poly)cyclic compounds. As part of our ongoing in- 2-alkynylbenzylidene ketones or malonates triggered
terest in the domino synthesis of functionalized het- by an external nucleophile has been demonstrated for
erocycles,[2] herein we report a novel and highly effi- the synthesis of highly substituted indanes.[8,9] As we
cient preparation of indane-fused 3,4-hydrocoumarin shall see, our endeavor in merging these two process-
that originates from unification between a phenol and es in a domino-fashion began with the identification
an o-alkynyl cinnamate via a formal hydroarylation– of an effective Lewis/Brønsted acid promoter.
À
À
cyclization process. Indane-fused 3,4-hydrocoumarins
In view of the series of bond-forming events as de-
are found in a wide collection of natural and designed picted in Scheme 1a, both the cinnamate and the
substances, best known by the brazilin family of natu- alkyne are anticipated to undergo nucleophilic attack,
ral dyes (Scheme 1a).[3] Furthermore, functionalized presumably facilitated through Lewis/Brønsted acid
3,4-dihydrocoumarins[4] and indanes[5] are also valua- activation of the respective functionalities. While it is
ble chemical entities in their own right. A cursory possible to envisage a co-catalyst system with each of
survey of the reported syntheses of “brazilin-like” its constituents catering for the activation of the cin-
indane-fused 3,4-hydrocoumarins revealed that the namate and the alkyne, respectively, a single Lewis/
current methods largely required multi-step chemical Brønsted acid capable of activating both functionali-
operations from commercial starting materials ties would be more appealing synthetically. Further-
(Scheme 1b).[6] In view of the molecular diversity and more, for o-alkynyl cinnamate substrates bearing
the largely untapped physical and biological poten- a non-activated alkyne, the Lewis/Brønsted acid of
tials of these valuable structural motifs, an expedient choice should function both as an oxophilic acid and
synthetic protocol would be highly desirable.
as a p-acid.[10] With these mechanistic considerations
in mind, our initial studies began with ethyl (2-phe-
nylethynyl)cinnamate and 3-methoxyphenol as the
test substrates in search of a suitable bi-functional cat-
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Scheme 1. Brazilin family natural products and synthetic plan for their analogues.
alyst. However, despite extensive experimentations, scandium, copper(II), and platinum(II) triflate salts
only starting materials could be detected or isolated and TfOH only afforded monocyclized product 3aa in
after examining a wide variety of Lewis/Brønsted acid low to moderate yields. It is noteworthy that isolated
promoters and reaction conditions (Scheme 2). At 3aa could be further converted to 2aa in the presence
this juncture, we reasoned the lack of reactivity could of 5 mol% of SnACHTNUTRGNEUNG(OTf)2 at 1008C for 10 h in 99%
be remedied by introducing an additional carboxylate yield. We further hypothesized the nucleophilicitiy of
group to enhance the electrophilicity of the cinnamate 3-methoxyphenol could be enhanced with the intro-
olefin, and concomitantly provide a bi-dentate bind- duction of a base, however, addition of Na2CO3 had
ing site to the Lewis/Brønsted acid promoter.[7d,11] no noticeable effect and no reaction was observed in
Gratifyingly, the revised substrate (1a) underwent the absence of Sn
smooth coupling and ring formations with 3-methoxy- terestingly, the combination of SnCl2 and Sc
phenol in the presence of 5 mol% of Sn(OTf)2 to also afforded the product 2aa (Table 1, entries 8 vs.
afford compound 2aa in 74% yield (Table 1, 20), whereas SnCl2 alone was not an effective catalyst
entry 1).[12] In
(OTf)3 also proved effective for this (Table 1, entry 18). These findings are path-pointing
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
transformation (Table 1, entry 2), while ytterbium, for the necessity of a “cationic-Sn(II) like” character
Scheme 2.
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Domino Hydroarylation–Cyclization Reaction: One-Pot Synthesis of Indane-Fused 3,4-Dihydrocoumarins
Table 1. Optimization studies for the reaction of 1a with 3-
methoxyphenol.
under our optimized reaction conditions (for details,
see the Supporting Information).
While a variety of phenols could be employed for
this reaction (Table 2), a clear electronic dependence
was observed in which only naphthols and highly elec-
tron-rich phenols afforded the corresponding benzyli-
dene indane-fused 3,4-hydrocoumarins in good to
high yields. 3-Substituted phenols showed excellent
regioselectivity, leading to products originating from
nucleophilic addition at the less hindered C-4 position
(Table 2, entries 1, 4, 5, and 9). Of all amine-contain-
ing phenols examined, NHCO2Et was the uniquely ef-
fective (Table 2, entry 9) while substrates bearing free
NH2, NMe2, and NHBoc substituents were unreactive.
It is noteworthy that, in all cases, only E isomers of
the cyclized products were obtained stereoselectively.
The structures of the cyclized products were inferred
based on an X-ray crystallographic analysis of 2ac[13]
as well as by 1H NMR analysis.
Entry
Catalyst
1a
2aa
3aa
[%][a]
[%][a]
[%][a]
Next, o-alkynyl cinnamates with varying aryl and
alkyne substitutions were examined (Table 3, en-
tries 1–23). In general, the reactions proceeded un-
eventfully to generate the corresponding methylenein-
dane-fused 3,4-hydrocoumarins irrespective of the
aryl substitution. Both terminal and internal alkynes
were well tolerated for this reaction, where internal
alkynes showed little electronic and/or steric depend-
ence. Functional group compatibility for the devel-
oped protocol was also demonstrated for methoxy, hy-
droxy, halogen, cyclopropyl, ester, and nitro contain-
ing compounds, with the exception of desilylation for
the TMS-substituted alkyne (1o). The E isomers of
the cyclized products were obtained exclusively in
most cases, apart from substrates 1c and 1d (Table 3,
entries 2 and 3) and alkyl-substituted (Table 3, en-
tries 16–22) alkynes. The structural validity of all
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Sn
In(OTf)3
Bi(OTf)3
Mg(OTf)2
Zn(OTf)2
Fe(OTf)3
Yb(OTf)3
Sc(OTf)3
Cu(OTf)2
A
–
–
80 (74)
70
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
35
70
10
–
N
R
100
100
100
100
65
–
90
100
100
90
N
N
N
R
E
G
AgOTf
Ph3PAuCl/AgOTf (1:1)
PtCl2/AgOTf (1:2)
TfOH
–
10
10
–
trace
–
–
–
–
–
20
–
trace
11
7
90
CF3CO2H
100
trace
24
100
100
7
8
27
100
–
27
15[b]
16[b,c]
17[b,c]
18
Sn
Sn
–
U
92 (90)
76
–
1
SnCl2
SnCl2/In
SnCl2/Sc
–
products were supported by H NMR, NOE experi-
19[b]
20[b]
21[b,d]
22[b,e]
23[b,f]
24[b,g]
25[b,h]
G
80
80
44
–
75
44
80
ments (compounds 2ca, 2da, 2qa, and 2ra), and X-ray
crystallographic analysis (compounds 2ac and 2qa).[13]
This process was effective for both diethyl and di-
methyl malonate-derived substrates, however, di-tert-
butyl malonate-derived substrate (1w) only afforded
the monocyclized product (4w) where the reaction
terminated after initial hydroarylation followed by de-
carboxylation (Table 3, entry 24). When one of the
carboxylates was replaced with a ketone and irrespec-
tive of the olefinic geometry, our standard reaction
conditions afforded the naphthalene derivatives 6 in
close analogy to Zhangꢁs report.[14] However, carrying
out the reaction at ambient temperature generated
benzopyran compounds 5 presumably via a Friedel–
Craft/dehydrative cyclization process, and attempts to
improve this reaction or induce further cyclization
were unsuccessful [Eq. (1) and Eq. (2)].[15a–b] Lastly,
cyano substrate 1z also underwent the domino hydro-
G
Sn
Sn
Sn
Sn
Sn
N
trace
[a]
1
Yields were determined by H NMR using trichloroethy-
lene as an internal standard. Values in parentheses indi-
cate isolated yields.
Using 1.2 equiv. 3-methoxyphenol for 24 h.
With 1.2 equiv. Na2CO3 as an additive.
In toluene.
In THF.
At 1208C for 16 h.
At 808C for 24 h.
With 3 mol% SnACHTNUGTRNEG(NUN OTf)2.
[b]
[c]
[d]
[e]
[f]
[g]
[h]
for the reaction to take place. Ultimately, product 2aa arylation–cyclization to give product 2ea, albeit in
could be obtained in 90% yield (Table 1, entry 15) a modest 33% yield [Eq. (3)].[15c]
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Table 2. SnACHTUNGTRENNUNG(OTf)2-catalyzed domino reaction of 1a with various phenols.
Entry
1
Phenol
Time [h]
24
Product
Yield [%][a]
3-methoxyphenol
90
2
3,5-dimethoxyphenol
12
93
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Domino Hydroarylation–Cyclization Reaction: One-Pot Synthesis of Indane-Fused 3,4-Dihydrocoumarins
Table 2. (Continued)
Entry
3
Phenol
Time [h]
Product
Yield [%][a]
3,4,5-trimethoxyphenol
8
96
4
5
6
sesamol
18
18
13
98
71
76
resorcinol
2-methylresorcinol
7
1-naphthol
24
84
8[b]
2-naphthol
24
28
76
69
9[b,c]
N-ethoxycarbonyl-3-aminophenol
[a]
Isolated yield.
Performed at 1208C.
With 20 mol% Sn(OTf)2.
[b]
[c]
AHCTUNGTRENNUNG
Although the precise mechanism for this reaction is with phenol to afford intermediate B (Scheme 3).
yet to be fully elucidated, we believe that the opening Subsequent lactonization followed by an intramolecu-
step of this domino process involved an initial hydro- lar nucleophilic addition of the so-obtained 1,3-dicar-
arylation of a SnACTHNUTRGNEUNG
(OTf)2-activated intermediate (A) boxylate (presumably as its Sn enolate[12d,g]) onto the
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Table 3. SnACHTUNGTRENNUNG(OTf)2-catalyzed domino hydroarylation-cyclization reaction of 1 with phenols.
Entry Substrate
Time Product (Yield)[a]
[h]
Entry Substrate
Time Product (Yield)[a]
[h]
1
1
13
5
2
3
9
14
15
2
4
13
4
5
11
21
16
17
15
13
6
17
18
9
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Domino Hydroarylation–Cyclization Reaction: One-Pot Synthesis of Indane-Fused 3,4-Dihydrocoumarins
Table 3. (Continued)
Entry Substrate
Time Product (Yield)[a]
[h]
Entry Substrate
Time Product (Yield)[a]
[h]
7
10
19[c]
24
8
4
20
21
22
3
9
8
3
10
15
23
11
23
23
4
12
8
24
3
[a]
Isolated yield.
[b]
1
The ratio of two inseparable isomers was determined by H NMR.
Performed at 1208C.
[c]
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Scheme 3. Possible mechanism for the SnACTHUNTRGNE(UNG OTf)2-catalyzed domino hydroarylation–cyclization reaction.
activated alkyne (C) led to the indane ring-closure, sulting mixture was stirred at 1008C for the reported time.
After the reaction was completed, the reaction mixture was
cooled to room temperature, diluted with CH2Cl2, succes-
sively washed with 1N NaOH solution and distilled water,
and extracted with CH2Cl2 (three times). The combined or-
ganic layer was dried over MgSO4 and concentrated under
vacuum. The residue was purified by column chromatogra-
phy on silica gel to afford the corresponding product 2.
and proto-destannylation to give the methylenein-
dane-fused 3,4-hydrocoumarin 2. A coordinated tran-
sition state as depicted by intermediate C could be in-
voked in close analogy to those previously reported
by Yamazaki and co-workers.[10b–d] The preferential
formation of the E isomer could be accounted for
through a conformation where steric interactions are
minimized.
(E)-Ethyl
7-benzylidene-3-methoxy-6-oxo-6,6a,7,11b-
tetrahydroindenoAHCTUNGTERG[NNUN 2,1-c]chromene-6a-carboxylate (2aa):
Brown oil (EtOAc:n-hexane=1:5). 1H NMR (CDCl3,
400 MHz): d=1.23 (t, J=7.2 Hz, 3H), 3.81 (s, 3H), 4.26 (q,
J=7.2 Hz, 2H), 5.05 (s, 1H), 6.64 (d, J=2.4 Hz, 1H), 6.80
(dd, J=2.4, 8.8 Hz, 1H), 6.91 (s, 1H), 7.01 (t, J=7.6 Hz,
1H), 7.11 (d, J=7.2 Hz, 1H), 7.17 (t, J=7.4 Hz, 1H), 7.21
(d, J=8.0 Hz, 1H), 7.30–7.38 (m, 4H), 7.48 (d, J=7.2 Hz,
2H); 13C NMR (CDCl3, 100 MHz): d=14.0, 48.8, 55.5, 62.7,
66.3, 102.4, 111.3, 112.0, 123.9, 124.7, 127.6, 127.8, 128.4,
128.5, 128.8, 129.0, 129.8, 136.3, 136.5, 138.1, 143.8, 151.0,
160.2, 164.9, 168.6; HR-EI-MS: m/z=426.1470 (M)+, calcd
for C27H22O5: 426.1467.
Conclusion
In summary, we have developed a SnACTHNUTRGENUN(G OTf)2-catalyzed
domino hydroarylation–cyclization reaction to access
a wide variety of methyleneindane-fused 3,4-hydro-
coumarins. The success of this reaction featured the
application of a judiciously selected bi-functional
Lewis acidic catalyst to promote two ring-closing
events as a single-pot operation. In view of the rela-
tively unexplored physical and biological potential of
indane-fused 3,4-hydrocoumarins, and their tradition-
al syntheses that generally required lengthy chemical Acknowledgements
manipulations, the technology described herein
This work was supported by both Basic Science Research
should enable a rapid entry to a diverse collection of
polycyclic “brazilin-like” analogues for further inves-
tigations.
Program and Nano·Material Technology Department Pro-
gram through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and
Technology (Nos. 2010–0007737, 2012R1A1A2041471, and
2012M3A7B4049654). We thank Dr. Ji-Eun Lee (Central In-
strument Facility, Gyeongsang National University) and
KBSI for X-ray crystallographic analysis.
Experimental Section
General Procedure for Sn
ACHTUNGRTEN(NUNG OTf)2-Catalyzed Domino
Reaction of 1 with Phenols
To a solution of 1 and phenol (1.2 equiv.) in ClCH2CH2Cl
(0.1M) in sealed vial was added Sn(OTf)2 (5 mol%). The re-
AHCTUNGTRENNUNG
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References
W. Yu, Bioorg. Med. Chem. Lett. 2007, 17, 2849; e) S.
Kesavan, J. S. Panek, J. A. Porco Jr, Org. Lett. 2007, 9,
5203; f) S. Hudson, M. Kiankarimi, W. Eccles, Y. S.
Mostofi, M. J. Genicot, W. Dwight, B. A. Fleck, K.
Gogas, W. S. Wade, Bioorg. Med. Chem. Lett. 2008, 18,
4495; g) P. Camps, X. Formosa, C. Galdeano, T.
Gꢃmez, D. MuÇoz-Torrero, M. Scarpellini, E. Viayna,
A. Badia, M. V. Clos, A. Camins, M. Pallꢄs, M. Bartoli-
ni, F. Mancini, V. Andrisano, J. Estelrich, M. Lizondo,
A. Bidon-Chanal, F. J. Luque, J. Med. Chem. 2008, 51,
3588.
[1] For reviews, see: a) L. F. Tietze, G. Brasche, K. Gerike,
(Eds.), Domino Reactions in Organic Synthesis, Wiley-
VCH, Weinheim, 2006; b) L. F. Tietze, Chem. Rev.
1996, 96, 115; c) K. C. Nicolaou, T. Montagnon, S. A.
Snyder, Chem. Commun. 2003, 551; d) J.-C. Wasilke,
S. J. Obrey, R. T. Baker, G. C. Bazan, Chem. Rev. 2005,
105, 1001; e) H.-C. Guo, J.-A. Ma, Angew. Chem. 2006,
118, 362; Angew. Chem. Int. Ed. 2006, 45, 354; f) D.
Enders, C. Grondal, M. R. M. Hꢂttl, Angew. Chem.
2007, 119, 1590; Angew. Chem. Int. Ed. 2007, 46, 1570;
g) T. Miura, M. Murakami, Chem. Commun. 2007, 217;
h) N. T. Patil, Y. Yamamoto, Synlett 2007, 1994; i) S. W.
Youn, Eur. J. Org. Chem. 2009, 2597.
[6] For examples of synthesis of brazilin-like compounds,
see: a) C. Pan, X. Zeng, Y. Guan, X. Jiang, L. Li, H.
Zhang, Synlett 2011, 425; b) H. Ishii, H. Koyama, K.
Hagiwara, T. Miura, G. Xue, Y. Hashimoto, G. Kita-
hara, Y. Aida, M. Suzuki, Bioorg. Med. Chem. Lett.
2012, 22, 1469.
[7] For selected examples, see: a) C. Jia, D. Piao, T. Kita-
mura, Y. Fujiwara, J. Org. Chem. 2000, 65, 7516; b) S.
Aoki, C. Amamoto, J. Oyamada, T. Kitamura, Tetrahe-
dron 2005, 61, 9291; c) K. Li, L. N. Foresee, J. A. Tunge,
J. Org. Chem. 2005, 70, 2881; d) S. Duan, R. Jana, J. A.
Tunge, J. Org. Chem. 2009, 74, 4612.
[8] Domino cyclization triggered by conjugate addition to
a,b-unsaturated carbonyl moiety: a) K. Gao, J. Wu,
Org. Lett. 2008, 10, 2251; b) Y. Shi, J. Huang, Y.-F.
Yang, L.-Y. Wu, Y.-N. Niu, P.-F. Huo, X.-Y. Liu, Y.-M.
Liang, Adv. Synth. Catal. 2009, 351, 141; c) G. Qiu, Q.
Ding, Y. Peng, J. Wu, Tetrahedron Lett. 2010, 51, 4391;
d) G. Qiu, Q. Ding, K. Gao, Y. Peng, J. Wu, ACS
Comb. Sci. 2011, 13, 13; e) D. Zheng, S. Li, Y. Luo, J.
Wu, Org. Lett. 2011, 13, 6402. Using activated enyne
substrates for the synthesis of methylenecyclopentanes:
f) G. Balme, D. Bouyssi, N. Coia, Eur. J. Org. Chem.
2007, 3158; g) D. Bouyssi, N. Monteiro, G. Balme, Tet-
rahedron Lett. 1999, 40, 1297.
[9] Synthesis of indenes via domino cyclization triggered
by 1,2-addition across the alkyne moiety: a) S. Ye, K.
Gao, H. Zhou, X. Yang, J. Wu, Chem. Commun. 2009,
5406; b) F. Zhou, X. Han, X. Lu, J. Org. Chem. 2011,
76, 1491.
[10] a) R. Takita, Y. Fukuta, R. Tsuji, T. Ohshima, M. Shi-
basaki, Org. Lett. 2005, 7, 1363; b) S. Morikawa, S. Ya-
mazaki, Y. Furusaki, N. Amano, K. Zenke, K. Kakiu-
chi, J. Org. Chem. 2006, 71, 3540; c) S. Morikawa, S.
Yamazaki, M. Tsukada, S. Izuhara, T. Morimoto, K.
Kakiuchi, J. Org. Chem. 2007, 72, 6459; d) S. Yamazaki,
S. Morikawa, K. Miyazaki, M. Takebayashi, Y. Yama-
moto, T. Morimoto, K. Kakiuchi, Y. Mikata, Org. Lett.
2009, 11, 2796.
[2] a) S. W. Youn, J.-H. Song, D.-I. Jung, J. Org. Chem.
2008, 73, 5658; b) J. O. Park, S. W. Youn, Org. Lett.
2010, 12, 2258.
[3] a) C.-K. Moon, S.-H. Lee, J.-H. Chung, S.-G. Kim, M.-
K. Chung, C.-H. Moon, Arch. Pharmacal Res. 1990, 13,
355; b) R. L. LaFemina, P. L. Graham, K. LeGrow,
J. C. Hastings, A. Wolfe, S. D. Young, E. A. Emini, D. J.
Hazuda, Antimicrob. Agents Chemother. 1995, 39, 320;
c) M.-K. Chung, C.-H. Choi, Korean J. Med. Chem.
1997, 7, 96; d) G. S. Hwang, J. Y. Kim, T. S. Chang,
S. D. Jeon, D. S. So, C. K. Moon, Arch. Pharmacal Res.
1998, 21, 774; e) M. S. Mok, S. D. Jeon, K. M. Yang,
D. S. So, C. K. Moon, Arch. Pharmacal Res. 1998, 21,
769; f) R. L. Tolman, A. C. Chin, W.O. Patent
0,193,864, 2001; g) W. Mar, H.-T. Lee, K.-H. Je, H.-Y.
Choi, E.-K. Seo, Arch. Pharmacal Res. 2003, 26, 147;
h) B.-M. Choi, B.-R. Kim, Eur. J. Pharmacol. 2008, 580,
12; i) C.-M. Hu, Y.-H. Liu, K.-P. Cheah, J.-S. Li, C.-
S. K. Lam, W.-Y. Yu, C.-S. Choy, J. Ethnopharmacol.
2009, 121, 79; j) T. Suzuki, N. Yamamoto, M. Nonaka,
S. Takeshima, Y. Hashimoto, G. Matsuda, M. Matsuya-
ma, T. Igarashi, T. Miura, R. Tanaka, S. Kato, Y. Aida,
Biochem. Biophys. Res. Commun. 2009, 380, 838; k) C.-
T. Yen, K. Nakagawa-Goto, T.-L. Hwang, P.-C. Wu, S.-
L. Morris-Natschke, W.-C. Lai, K. F. Bastow, F.-R.
Chang, Y.-C. Wu, K.-H. Lee, Bioorg. Med. Chem. Lett.
2010, 20, 1037.
[4] a) F. Asai, M. Iinuma, T. Tanaka, M. Mizuno, Phyto-
chemistry 1991, 30, 3091; b) F. Asai, M. Iinuma, T.
Tanaka, M. Takenaka, M. Mizuno, Phytochemistry
1992, 31, 2487; c) J. Posakony, M. Hirao, S. Stevens,
J. A. Simon, A. Bedalov, J. Med. Chem. 2004, 47, 2635;
d) F. Song, S. Lu, J. Gunnet, J. Z. Xu, P. Wines, J.
Proost, Y. Liang, C. Baumann, J. Lenhard, W. V.
Murray, K. T. Demarest, G.-H. Kuo, J. Med. Chem.
2007, 50, 2807; e) F. Ulgheri, M. Marchetti, O. Piccolo,
J. Org. Chem. 2007, 72, 6056; f) J. F. Teichert, B. L. Fer-
inga, Chem. Commun. 2011, 47, 2679; g) S. Peng, L.
Wang, H. Guo, S. Sun, J. Wang, Org. Biomol. Chem.
2012, 10, 2537, and references cited therein.
[11] a) N. T. Patil, Y. Yamamoto, Synlett 2007, 1994; b) C.
Fallan, P. F. Quigley, H. W. Lam, J. Org. Chem. 2011,
76, 4112.
[12] For selected examples of SnACHTNUGRTENUNG(OTf)2-catalyzed reactions,
see: a) T. Mukaiyama, T. Shimpuku, T. Takashima, S.
Kobayashi, Chem. Lett. 1989, 18, 145; b) S. Kobayashi,
H. Uchiro, Y. Fujishita, I. Shiina, T. Mukaiyama, J. Am.
Chem. Soc. 1991, 113, 4247; c) G. Sekar, V. K. Singh, J.
Org. Chem. 1999, 64, 287; d) A. J. Macꢅas-Sꢆnchez,
C. F. D. Amigo, I. G. Collado, Synlett 2003, 1989; e) M.
Shi, M. Jiang, L.-P. Liu, Org. Biomol. Chem. 2007, 5,
438; f) A. S. Dudnik, A. W. Sromek, M. Rubina, J. T.
[5] a) C. R. Ganellin, Adv. Drug Res. 1967, 4, 163; b) H.
Ho, S. P. Hollinshead, S. E. Hall, K. Kalter, L. M.
Ballas, Bioorg. Med. Chem. Lett. 1996, 6, 973; c) S.
Ulmschneider, U. Mꢂller-Vieira, C. D. Klein, I. Antes,
T. Lengauer, R. W. J. Hartmann, J. Med. Chem. 2005,
48, 1563; d) M. F. Gross, S. Beaudoin, G. McNaughton-
Smith, G. S. Amato, N. A. Castle, C. Huang, A. Zou,
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
9
ÞÞ
These are not the final page numbers!

Jin Hyuck Joo and So Won Youn
FULL PAPERS
Kim, A. V. Kel’in, V. Gevorgyan, J. Am. Chem. Soc.
2008, 130, 1440; g) G. Mancilla, M. Femenꢅa-Rꢅos, A. J.
Macꢅas-Sꢆnchez, I. G. Collado, Tetrahedron 2008, 64,
11732; h) J. Dai, J. Wu, G. Zhao, W.-M. Dai, Chem.
Eur. J. 2011, 17, 8290; i) Z. Chen, Z. Tian, J. Zhang, J.
Ma, J. Zhang, Chem. Eur. J. 2012, 18, 8591.
Cambridge
Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[14] L. Liu, L. Wei, J. Zhang, Adv. Synth. Catal. 2010, 352,
1920.
[15] For selected examples, see: a) X.-S. Wang, C.-W.
Zheng, S.-L. Zhao, Z. Chai, G. Zhao, G.-S. Yang, Tetra-
hedron: Asymmetry 2008, 19, 2699; b) Y.-C. Wu, L. Liu,
Y.-L. Liu, D. Wang, Y.-J. Chen, J. Org. Chem. 2007, 72,
9383; c) S. R. Kolla, Y. R. Lee, Tetrahedron 2011, 67,
8271.
[13] CCDC 896099 (2ac) and CCDC 896098 (2qa) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
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Domino Hydroarylation–Cyclization Reaction: One-Pot
Synthesis of Indane-Fused 3,4-Dihydrocoumarins
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