Multicatalytic tandem reactions of 2-alkynylbenzaldoximes with isocyanides

Article abstract of DOI:10.1002/adsc.200900442

An efficient tandem reaction of 2-alkynylbenzaldoximes with isocyanides co-catalyzed by silver triflate and bismuth triflate has been developed, which gives rise to the unexpected JV-(isoquinolin-l-yl)formamides in good to excellent yields. The iodo- and

Full text of DOI:10.1002/adsc.200900442

FULL PAPERS
DOI: 10.1002/adsc.200900442
Multicatalytic Tandem Reactions of 2-Alkynylbenzaldoximes with
Isocyanides
Zhiyuan Chen,a Xingxin Yu,a Mingchao Su,a Xiaodi Yang,c and Jie Wua,b,*
a
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, Peopleꢀs Republic of China
Fax : (+86)-216-510-2412; e-mail: jie_wu@fudan.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 354 Fenglin Road, Shanghai 200032, Peopleꢀs Republic of China
Laboratory of Advanced Materials, Fudan University, 220 Handan Road, Shanghai 200433, Peopleꢀs Republic of China
c
Received: June 25, 2009; Revised: September 30, 2009; Published online: October 28, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900442.
Abstract: An efficient tandem reaction of 2-alkynyl- obtained as well by variation of the reaction condi-
benzaldoximes with isocyanides co-catalyzed by tions.
silver triflate and bismuth triflate has been devel-
oped, which gives rise to the unexpected N-(isoqui- Keywords: 2-alkynylbenzaldoximes; bismuth triflate;
nolin-1-yl)formamides in good to excellent yields. isocyanides; N-(isoquinolin-1-yl)formamides; silver
The iodo- and bromo-containing products could be triflate
Introduction
hibit remarkable biological activities.[7,8] Moreover,
isoquinoline derivatives have found applications as
The chemical genetics approach has created a critical chiral ligands for transition metal catalysts.[9] In addi-
demand to develop practical routes for rapid synthesis tion, their iridium complexes have been demonstrated
of natural product-like molecules.[1] Among the diver- to be useful in organic light-emitting diodes.[10] Thus,
sity-oriented synthesis strategies, the development of continuous efforts have been made for the develop-
tandem reactions[2] for the efficient construction of ment of new methods for the synthesis of isoquino-
small molecules is an important part from the view- lines.[11,12] Although there are several routes to isoqui-
points of operational simplicity and assembly efficien- nolines, the development of efficient methodologies
cy. Meanwhile, much attention has been paid to the for the synthesis of functionalized isoquinolines under
multicatalytic processes in the field of tandem reac- mild conditions is still of high interest. Herein, we dis-
tions.[3,4] Usually, in a single flask one or more cata- close an unusual multicatalytic tandem reaction of 2-
lysts promote two or more distinct chemical transfor- alkynylbenzaldoximes with isocyanides, which affords
mations in a reaction. Recently, we have developed the unexpected N-(isoquinolin-1-yl)formamide in
multicatalytic systems for the generation of nitrogen- good to excellent yields.
containing heterocycles.[5] For instance, the combina-
Recently, 2-alkynylbenzaldoximes have been re-
tion of silver triflate and proline catalysis shows high ported as a versatile building block for the synthesis
efficiency in the multicomponent reactions of 2-alky- of nitrogen-containing heterocycles.[6a,b,13] For exam-
nylbenzaldehydes, amines, and ketones.[5a] The one- ple, Shin disclosed the gold-catalyzed internal redox/
pot reaction of 2-alkynylbenzaldehydes, amines, zinc, dipolar cycloaddition cascade reactions of 2-
and allylic bromide or benzyl bromide could not pro- alkynylbenzaldox
ceed without the co-catalyst Mg(ClO4)2 and Cu- lization-[3+2]cycloaddition-rearrangement reaction
imes.[13a] A tandem electrophilic cyc-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
(OTf)2.[5b] As part of a continuing effort in our labora- of 2-alkynylbenzaldoximes with DMAD in the pres-
tory for accessing privileged scaffolds,[6] we have been ence of bromine was developed as well.[6a] We noticed
interested in exploring the new multicatalytic tandem that during the reaction process, the 2-alkynylbenzal-
processes to facilitate the preparation of natural prod- doxime could easily transfer to the isoquinoline N-
uct-like compounds.
oxide in the presence of suitable Lewis acids or elec-
It is well known that the isoquinoline core exists in trophiles (Scheme 1).[6a,b,13] Prompted by these results
many natural products and pharmaceuticals that ex- and the advancement of isocyanide chemistry,[14] we
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AHCTUNGTREGfNNUN ormamide 4a. Addition of zinc triflate as catalyst
dramatically improved the yield of the product (68%
yield, Table 1, entry 2). Further screening of solvents
demonstrated that 1,4-dioxane was the best choice for
this transformation (72% yield, Table 1, entry 6). Dif-
ferent Lewis acids were examined as catalyst subse-
quently. The yield increased to 83% when bismuth tri-
flate was utilized in the reaction (Table 1, entry 9).
Moreover, the reaction time was shortened to 12 h
Scheme 1. Electrophile-mediated or Lewis acid-catalyzed
cyclization of 2-alkynylbenzaldoxime 1.
conceived that isocyanides might be a good partner in under these conditions. Inferior results were displayed
the tandem reaction of 2-alkynylbenzaldoximes. Thus, when other Lewis acids were employed in the reac-
we started to explore the possibility of this transfor- tion. For example, only a 20% yield of product 4a was
mation.
isolated when silver triflate was used as catalyst
(Table 1, entry 11). Similar yields were afforded when
the catalytic amount of bismuth triflate was reduced
to 1–5 mol% (Table 1, entries 13–15). Different
Brønsted acid catalysts (10 mol%) were examined as
Results and Discussion
As described above,[13] in the presence of a Lewis acid well (data not shown in Table 1). No reaction oc-
isoquinoline N-oxides could be easily obtained via curred or only a trace amount of product 4a was de-
electrophilic cyclization of 2-alkACTHNUTRGENUGyN nylbenzaldoximes. In tected in the presence of TsOH, TfOH, HOAc, or
order to simplify the tandem reaction process of 2-al- HCl. The desired product 4a could be isolated with
kynylbenzaldoximes with isocyanide, initially the re- 31% yield when the reaction was co-catalyzed by
action of isoquinoline N-oxide 2a with 4-methoxy- TsOH (10 mol%) and Bi
phenyl isocyanide 3a was performed. This reaction oc- no desired product was generated when the reaction
curred in toluene at room temperature to generate an was performed in the presence of Bi(OTf)3 (2 mol%)
ACHTUNGRTEN(NUNG OTf)3 (2 mol%). However,
AHCTUNGTRENNUNG
unexpected product in 10% yield (Table 1, entry 1). with other acids (TfOH, HOAc, HCl). With this
Structural identification revealed that the compound promising result in hands, we started to investigate
obtained was the unexpected N-(isoquinolin-1-yl)- the one-pot tandem reaction of 2-alkynylbenzaldox-
Table 1. Screening conditions for the reaction of isoquinoline N-oxide 2a with isocyanide 3a.
Entry
Lewis acid
nono
Solvent
Time [h]
Yield [%][a]
1
2
3
4
5
6
7
8
toluene
toluene
DCE
THF
DMF
1,4-dioxane
NMP
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
48
60
60
60
60
60
60
60
12
60
60
60
12
18
24
10
68
56
NR
NR
72
61
71
83
61
20
74
84
86
83
Zn
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Cu(OTf)2
(OTf)3
(OTf)3
A
N
R
N
G
ACHTUNGTRENNUNG
R
9
Bi
Sc
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
10
11
12
13[b]
14[c]
15[d]
AgOTf
Yb(OTf)3
(OTf)3
(OTf)3
(OTf)3
AHCTUNGTRENNUNG
Bi
Bi
Bi
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
[a]
Isolated yield based on isoquinoline N-oxide 2a.
[b]
[c]
[d]
In the presence of 5 mol% of Bi
In the presence of 2 mol% of Bi
In the presence of 1 mol% of BiAHCTNUGTRENNNUG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
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Scheme 2. Possible mechanism for the tandem reactions of 2-alkynylbenzaldoximes 1 with isocyanides 3.
ime 1a with 4-methoxyphenyl isocyanide 3a. Since bis- 65% and 67% yields, respectively (Table 2, entries 2
muth triflate was not effective for the transformation and 3). The conditions have proven to be useful for
of 2-alkynylbenzaldoxime 1a and silver triflate was other aryl isocyanides as well. For example, an excel-
the best one for the generation of isoquinoline N- lent yield was observed in the reaction of 4-methyl-
oxide 2a, the combination of silver triflate and bis- phenyl isocyanide 3c with 2-alkynylbenzaldoxime 1a
muth triflate was tested in the reaction 2-alkynylben- or 1e (Table 2, entries 9 and 12). Alkyl isocyanides
zaldoxime 1a with 4-methoxyphenyl isocyanide 3a. To are also suitable partners in this process. As expected,
our delight, a 94% yield of compound 4a was ob- an almost quantitative yield of compound 4m was iso-
tained when the reaction occurred in the presence of lated for the reaction of 2-alkynylbenzaldoxime 1a
silver triflate (5 mol%) and bismuth triflate (2 mol%) with tert-butyl isocycanide 3d (Table 2, entry 13). Re-
in 1,4-dioxane at room temperature. Although the action of cyclohexyl isocyanide 3e with 2-alkynylben-
first step of the reaction has already been known,[6b] zaldoxime 1a or 1e worked well to generate the de-
this tandem reaction via a concomitant process pro- sired N-(isoquinolin-1-yl)formamide in good yield
vided an efficient way for diversity and complexity (Table 2, entries 17 and 18). 2-Alkynylbenzaldoxime
generation starting from easily accessible materials. 1a reacted with 1-octyl isocyanide 3f leading to the
For this tandem reaction, we reasoned that 2-alkynyl- desired product 4s in 82% yield (Table 1, entry 19).
benzaldoxime 1 was converted to isoquinoline N-
oxide 2 firstly. The subsequent nucleophilic addition alkACHTUNGTRENNUNG
The electrophile involved cascade reactions of 2-
ynylbenzaldoximes 1 with isocyanides 3 were in-
of isocyanide to isoquinoline N-oxide 2 would afford vestigated subsequently [Scheme 3, Eq. (1)]. Iodo-
intermediate A, which then underwent intramolecular containing N-(isoquinolin-1-yl)formamide 5a was iso-
cyclization to generate the intermediate B. After rear- lated in 96% yield in the reaction of 2-alkynylbenzal-
rangement, N-(isoquinolin-1-yl)formamide 4 would be doxime 1a with 4-methoxyphenyl isocyanide 3a. The
formed (Scheme 2).
structure of 5a was verified by X-ray diffraction anal-
The scope of this transformation was then explored ysis meanwhile (Figure 1). A similar result was ob-
under the optimized conditions [silver triflate tained when 4-methylphenyl isocyanide 3c was uti-
(5 mol%), bismuth triflate (2 mol%), 1,4-dioxane, lized as a replacement. Fluoro-substituted 2-alkynyl-
room temperature], and the results are summarized benzaldoxime 1e with 4-methoxyphenyl isocyanide 3a
in Table 2. For all cases, this multicatalytic tandem re- gave rise to the expected product 5c in 93% yield.
action proceeded smoothly leading to the correspond- Bromine also showed efficiency in the reaction of 2-
ing products 4 in good to excellent yields. With re- alkynylbenzaldoxime 1a with 1-octyl isocyanide 3f,
spect to 2-alkynylbenzaldoximes, the expected N-(iso- which generated the expected product 5d in 87%
quinolin-1-yl)formamides resulting from 4-methoxy- yield [Scheme 3, Eq. (2)]. However, NBS was not a
phenyl isocyanide 3a were obtained in good yields good partner in this transformation (data not shown
(Table 1, entries 1–6). For instance, 4-methoxyphenyl in Scheme 3).
isocyanide 3a reacted with 2-alkynylbenzaldoxime 1b
In conclusion, we have described efficient tandem
or 1c giving rise to the desired product 4b or 4c in reactions of 2-alkynylbenzaldoximes with isocyanides
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Table 2. Tandem reactions of 2-alkynylbenzaldoximes 1 with isocyanides 3 co-catalyzed by silver triflate and bismuth triflate.
Entry
R1/R2
R3
Yield [%][a]
1
2
3
4
5
6
7
8
H/C6H5 (1a)
5-F/n-Bu (1b)
5-F/cyclopropyl (1c)
H/cyclopropyl (1d)
5-F/C6H5 (1e)
5-F/4-MeOC6H5 (1f)
H/C6H5 (1a)
5-F/C6H5 (1e)
H/C6H5 (1a)
5-F/cyclopropyl (1c)
H/cyclopropyl (1d)
5-F/C6H5 (1e)
4-MeOC6H4 (3a)
4-MeOC6H4 (3a)
4-MeOC6H4 (3a)
4-MeOC6H4 (3a)
4-MeOC6H4 (3a)
4-MeOC6H4 (3a)
4-Et2NC6H4 (3b)
4-Et2NC6H4 (3b)
4-MeC6H4 (3c)
4-MeC6H4 (3c)
4-MeC6H4 (3c)
4-MeC6H4 (3c)
t-Bu (3d)
t-Bu (3d)
t-Bu (3d)
t-Bu (3d)
cyclohexyl (3e)
cyclohexyl (3e)
n-octyl (3f)
94 (4a)
65 (4b)
67 (4c)
54 (4d)
87 (4e)
62 (4f)
83 (4g)
75 (4h)
97 (4i)
75 (4j)
50 (4k)
98 (4l)
99 (4m)
72 (4n)
84 (4o)
94 (4p)
85 (4q)
84 (4r)
82 (4s)
9
10
11
12
13
14
15
16
17
18
19
H/C6H5 (1a)
5-F/cyclopropyl (1c)
H/cyclopropyl (1d)
5-F/C6H5 (1e)
H/C6H5 (1a)
5-F/C6H5 (1e)
H/C6H5 (1a)
[a]
Isolated yield based on 2-alkynylbenzaldoxime 1.
Scheme 3. Iodine- or bromine-mediated sequential reactions of 2-alkynylbenzaldoximes 1 with isocyanides 3.
co-catalyzed by silver triflate and bismuth triflate. taining products could be obtained as well by varia-
The N-(isoquinolin-1-yl)formamides were generated tion of the reaction conditions, which might undergo
in good to excellent yields. The iodo- or bromo-con- further elaboration via known palladium chemistry.
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Zhiyuan Chen et al.
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C23H18N2O2: C 77.95, H 5.12, N 7.90; found: C 77.91, H 5.36,
N 7.78.
General Procedure for Iodine- or Bromine-Mediated
Sequential Reactions of 2-Alkynylbenzaldoximes 1
with Isocyanides 3
A mixture of 2-alkynylbenzaldoxime 1 (0.2 mmol) and
iodine or bromine (0.2 mmol, 1.0 equiv.) in anhydrous 1,4-di-
oxane (2.0 mL) was stirred at room temperature under air
atmosphere for about 24 h, until 2-alkynylbenzaldoxime 1
was completely consumed. The reaction solution was diluted
with ethyl acetate (10 mL), washed with 0.65M Na2S2O3 so-
lution (10 mLꢂ3). The combined organic layer was washed
with saturated brine, dried over Na2SO4, and concentrated
under vacuum to afford a crude product. Anhydrous 1,4-di-
oxane (2.0 mL) was added to the crude product subsequent-
ly, to which was then added a mixture of bismuth triflate
(2 mol%) and isocyanide 3 (0.3 mmol, 1.5 equiv.) in 1,4-di-
oxane (0.1 mL) at 308C. After completion of the reaction as
indicated by TLC, the solvent was removed under reduced
pressure and the residue was purified on silica gel provided
the corresponding product 5.
Data of a selected example: N-(4-iodo-3-phenylisoquino-
lin-1-yl)-N-(4-methoxyphenyl)formamide (5a): 96% yield;
1H NMR (400 MHz, CDCl3): d=3.78 (s, 3H), 6.86–6.90 (m,
2H), 7.30 (d, J=8.7 Hz, 2H), 7.42–7.52 (m, 4H), 7.61–7.86
(m, 4H), 8.30 (d, J=8.2 Hz, 1H), 8.94 (s, 1H); 13C NMR
(100 MHz, CDCl3): d=56.0, 115.1, 126.0, 126.7, 126.8, 126.9,
128.5, 129.1, 129.2, 129.4, 129.5, 130.6, 133.0, 133.7, 141.5,
143.2, 152.1, 158.6, 163.2; HR-MS: m/z=481.0422, calcd. for
Figure 1. ORTEP drawing of compound 5a (30% probability
ellipsoids).
+
C23H17IN2O2 [M+H]+: 481.0413; elem. anal. calcd. for
Small library construction as well as biological screen-
ing of these small molecules is ongoing, and the re-
sults will be reported in due course.
C23H17IN2O2: C 57.52, H 3.57, N 5.83; found: C 57.39, H
3.66, N 5.71 (for details, please see Supporting Information)
CCDC 745747 contains the supplementary crystallograph-
ic data for compound 5a of this paper. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif or on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK [fax.: (internat.) + 44 1223/336–033; e-mail:
deposit@ccdc.cam.ac.uk].
Experimental Section
General Procedure for Tandem Reactions of 2-
Alkynylbenzaldoximes 1 with Isocyanides 3 Co-
Catalyzed by Silver Triflate and Bismuth Triflate
A mixture of 2-alkynylbenzaldoxime 1 (0.2 mmol) and silver
triflate (5 mol%) in anhydrous 1,4-dioxane (2.0 mL) was
heated to 708C for 1 hour. Then the solution was cooled to
room temperature. Bismuth triflate (2 mol%) and isocya-
nide 2 (0.3 mmol, 1.5 equiv.) in 1,4-dioxane (0.1 mL) were
added subsequently and the mixture was stirred at 308C.
After completion of the reaction as indicated by TLC, the
solvent was removed under reduced pressure and the resi-
due was purified on silica gel provided the corresponding
product 4.
Acknowledgements
Financial support from National Natural Science Foundation
of China (20772018), the Science and Technology Commis-
sion of Shanghai Municipality (09JC14049), and Program
for New Century Excellent Talents in University (NCET-07-
0208) is gratefully acknowledged.
Data of a selected example: N-(4-methoxyphenyl)-N-(3- References
1
phenylisoquinolin-1-yl)formamide (4a): 94% yield; H NMR
(400 MHz, CDCl3): d=3.77 (s, 3H), 6.88 (d, J=3.2 Hz, 2H),
7.33–7.55 (m, 6H), 7.58–7.81 (m, 2H), 7.89 (d, J=8.24 Hz,
1H), 8.10–8.16 (m, 3H), 9.05 (s, 1H); 13C NMR (100 MHz,
CDCl3): d=55.4, 114.4, 116.6, 122.9, 125.0, 126.3, 126.8,
127.6, 127.8, 128.8, 128.9, 130.7, 132.5, 138.1, 139.6, 149.4,
151.4, 157.9, 163.0; HR-MS: m/z=355.1436, calcd. for
[1] a) D. P. Walsh, Y.-T. Chang, Chem. Rev. 2006, 106,
2476; b) P. Arya, D. T. H. Chou, M.-G. Baek, Angew.
Chem. 2001, 113, 351; Angew. Chem. Int. Ed. 2001, 40,
339; c) S. L. Schreiber, Science 2000, 287, 1964.
[2] For reviews, see: a) J. Montgomery, Angew. Chem.
2004, 116, 3980; Angew. Chem. Int. Ed. 2004, 43, 3890;
b) E. Negishi, C. Copꢃret, S. Ma, S. Y. Liou, F. Liu,
+
C23H18N2O2 [M+H]+: 355.1447; elem. anal. calcd. for
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Multicatalytic Tandem Reactions of 2-Alkynylbenzaldoximes with Isocyanides
FULL PAPERS
Chem. Rev. 1996, 96, 365; c) L. F. Tietze, Chem. Rev.
1996, 96, 115; d) R. Grigg; V. Sridharan, J. Organomet.
Chem. 1999, 576, 65; e) T. Miura, M. Murakami, Chem.
Commun. 2007, 217. For recent examples, see: f) K.
Agapiou, D. F. Cauble, M. J. Krische, J. Am. Chem.
Soc. 2004, 126, 4528; g) K. Subburaj, J. Montgomery, J.
Am. Chem. Soc. 2003, 125, 11210; h) H.-C. Guo, J.-A.
Ma, Angew. Chem. 2006, 118, 362; Angew. Chem. Int.
Ed. 2006, 45, 354.
[8] a) D. Kletsas, W. Li, Z. Han, V. Papadopoulos, Bio-
chem. Pharmacol. 2004, 67, 1927; b) U. R. Mach, A. E.
Hackling, S. Perachon, S. Ferry, C. G. Wermuth, J.-C.
Schwartz, P. Sokoloff, H. Stark, ChemBioChem 2004, 5,
508; c) D. E. Muscarella, K. A. OꢀBrian, A. T. Lemley,
S. E. Bloom, Toxicol. Sci. 2003, 74, 66; d) F. Dzierszin-
ski, A. Coppin, M. Mortuaire, E. Dewally, C. Slomian-
ny, J.-C. Ameisen, F. Debels, S. Tomavo, Antimicrob.
Agents Chemother. 2002, 46, 3197.
[9] For selected examples, see: a) F. Durola, J.-P. Sauvage,
O. S. Wenger, Chem. Commun. 2006, 171; b) B. A.
Sweetman, H. Mꢄller-Bunz, P. J. Guiry, Tetrahedron
Lett. 2005, 46, 4643; c) C. W. Lim, O. Tissot, A. Matti-
son, M. W. Hooper, J. M. Brown, A. R. Cowley, D. I.
Hulmes, A. J. Blacker, Org. Process Res. Dev. 2003, 7,
379; d) N. W. Alcock, J. M. Brown, G. I. Hulmes, Tetra-
hedron: Asymmetry 1993, 4, 743.
[10] For selected examples, see: a) K.-H. Fang, L.-L. Wu,
Y.-T. Huang, C.-H. Yang, I.-W. Sun, Inorg. Chim. Acta
2006, 359, 441; b) S.-J. Liu, Q. Zhao, R.-F. Chen, Y.
Deng, Q.-L. Fan, F.-Y. Li, L.-H. Wang, C.-H. Huang,
W. Huang, Chem. Eur. J. 2006, 12, 4351; c) Q. Zhao, S.
Liu, M. Shi, C. Wang, M. Yu, L. Li, F. Li, T. Yi, C.
Huang, Inorg. Chem. 2006, 45, 6152; d) A. Tsuboyama,
H. Iwawaki, M. Furugori, T. Mukaide, J. Kamatani, S.
Igawa, T. Moriyama, S. Miura, T. Takiguchi, S. Okada,
M. Hoshino, K. Ueno, J. Am. Chem. Soc. 2003, 125,
12971.
[11] a) Q. Huang, R. C. Larock, J. Org. Chem. 2003, 68, 980;
b) G. Dai, R. C. Larock, J. Org. Chem. 2003, 68, 920;
c) G. Dai, R. C. Larock, J. Org. Chem. 2002, 67, 7042;
d) Q. Huang, J. A. Hunter, R. C. Larock, J. Org. Chem.
2002, 67, 3437; e) K. R. Roesch, R. C. Larock, J. Org.
Chem. 2002, 67, 86; f) K. R. Roesch, H. Zhang, R. C.
Larock, J. Org. Chem. 2001, 66, 8042; g) K. R. Roesch,
R. C. Larock, Org. Lett. 1999, 1, 553.
[12] For selected examples, see: a) M. Balasubramanian,
J. G. Keay, Isoquinoline Synthesis, in: Comprehensive
Heterocyclic Chemistry II, (Eds.: A. E. McKillop, A. R.
Katrizky, C. W. Rees, E. F. V. Scrivem), Elsevier,
Oxford, 1996, 5, p 245; b) For a review on the synthesis
of isoquinoline alkaloid, see: M. Chrzanowska, M. D.
Rozwadowska, Chem. Rev. 2004, 104, 3341; c) Y.-N.
Niu, Z.-Y. Yan, G.-L. Gao, H.-L. Wang, X.-Z. Shu, K.
G. Ji, Y.-M. Liang J. Org. Chem. 2009, 74, 2893; d) Y.-
Y. Yang, W.-G. Shou, Z.-B. Chen, D. Hong, Y.-G.
Wang, J. Org. Chem. 2008, 73, 3928; e) D. Fischer, H.
Tomeba, N. K. Pahadi, N. T. Patil, Z. Huo, Y. Yamamo-
to, J. Am. Chem. Soc. 2008, 130, 15720; f) M. Movassa-
ghi, M. D. Hill, Org. Lett. 2008, 10, 3485; g) T. Black-
burn, Y. K. Ramtohul, Synlett 2008, 1159; h) G. Pandey,
M. Balakrishnan, J. Org. Chem. 2008, 73, 8128; i) S. Su,
J. A. Porco, Org. Lett. 2007, 9, 4983; j) M. Mori, H. Wa-
kamatsu, K. Tonogaki, R. Fujita, T. Kitamura, Y. Sato,
J. Org. Chem. 2005, 70, 1066; k) Z. Xiang, T. Luo, K.
Lu, J. Cui, X. Shi, R. Fathi, J. Chen, Z. Yang, Org. Lett.
2004, 6, 3155; l) B. K. Ghorai, S. Duan, D. Jiang, J. W.
Herndon, Synthesis 2006, 3661; m) F. Palacios, C.
Alonso, M. Rodrꢅguez, de E. M. Marigorta, G. Ru-
biales, Eur. J. Org. Chem. 2005, 1795; n) F. Palacios, C.
Alonso, G. Rubiales, M. Villegas, Tetrahedron 2005, 61,
2779; o) T. K. Sarkar, N. Panda, S. Basak, J. Org.
[3] For selected recent reviews on multicatalysis, see: a) A.
Ajamian, J. L. Gleason, Angew. Chem. 2004, 116, 3842;
Angew. Chem. Int. Ed. 2004, 43, 3754; b) J. M. Lee, Y.
Na, H. Han, S. Chang, Chem. Soc. Rev. 2004, 33, 302;
c) J. C. Wasilke, O S. J. Brey, R. T. Baker, G. C. Bazan,
Chem. Rev. 2005, 105, 1001; d) D. Enders, C. Grondal,
M. R. Huttl, Angew. Chem. 2007, 119, 1590; Angew.
Chem. Int. Ed. 2007, 46, 1570; e) C. J. Chapman, C. G.
Frost, Synthesis 2007, 1; f) A. M. Walji, D. W. C. Mac-
Millan, Synlett 2007, 1477; g) C. Wang, Z. Xi, Chem.
Soc. Rev. 2007, 36, 1395.
[4] For recent selected examples, see: a) T. A. Cernak,
T. H. Lambert, J. Am. Chem. Soc. 2009, 131, 3124, and
references cited therein; b) B. D. Kelly, J. M. Allen,
R. E. Tundel, T. H. Lambert, Org. Lett. 2009, 11, 1381;
c) L.-Q. Lu, Y.-J. Cao, X.-P. Liu, J. An, C.-J. Yao, Z.-H.
Ming, W.-J. Xiao, J. Am. Chem. Soc. 2008, 130, 6946.
[5] a) Q. Ding, J. Wu, Org. Lett. 2007, 9, 4959; b) K. Gao,
J. Wu, J. Org. Chem. 2007, 72, 8611; c) Q. Ding, X. Yu,
J. Wu, Tetrahedron Lett. 2008, 49, 2752; d) Q. Ding, Z.
Wang, J. Wu, Tetrahedron Lett. 2009, 50, 198.
[6] a) Q. Ding, Z. Wang, J. Wu, J. Org. Chem. 2009, 74,
921; b) Q. Ding, J. Wu, Adv. Synth. Catal. 2008, 350,
1850; c) K. Gao, J. Wu, Org. Lett. 2008, 10, 2251; d) Q.
Ding, J. Wu, J. Comb. Chem. 2008, 10, 541; e) L.
Zhang, J. Wu, Adv. Synth. Catal. 2007, 349, 1047; f) Z.
Wang, R. Fan, J. Wu, Adv. Synth. Catal. 2007, 349,
1943; g) Q. Ding, Y. Ye, R. Fan, J. Wu, J. Org. Chem.
2007, 72, 5439; h) L. Zhang, T. Meng, R. Fan, J. Wu, J.
Org. Chem. 2007, 72, 7279; i) Z. Wang, B. Wang, J. Wu,
J. Comb. Chem. 2007, 9, 811.
[7] For selected examples, see: a) K. W. Bentley, The Iso-
quinoline Alkaloids, Harwood Academic, Australia,
1998, Vol. 1; b) B. W. Trotter, K. K. Nanda, N. R. Kett,
C. P. Regan, J. J. Lynch, G. L. Stump, L. Kiss, J. Wang,
R. H. Spencer, S. A. Kane, R. B. White, R. Zhang,
K. D. Anderson, N. J. Liverton, C. J. McIntyre, D. C.
Eshore, G. D. Hartman, C. J. Dinsmore, J. Med. Chem.
2006, 49, 6954; c) P. Ramesh, N. S. Reddy, Y. Venkates-
warlu, J. Nat. Prod. 1999, 62, 780; d) S. Oi, K. Ikedou,
K. Takeuchi, M. Ogino, Y. Banno, H. Tawada, T.
Yamane, PCT Int. Appl. WO 2002062764A1, 2002;
e) T. Kaneda, Y. Takeuchi, H. Matsui, K. Shimizu, N.
Urakawa, S. Nakajyo, J. Pharmacol. Sci. 2005, 98, 275;
f) Y. Mikami, K. Yokoyama, H. Tabeta, K. Nakagaki,
T. Arai, J. Pharm. Dyn. 1981, 4, 282; g) C. Marchand,
S. Antony, K. W. Kohn, M. Cushman, I A. Oanoviciu,
B. L. Staker, A. B. Burgin, L. Stewart, Y. Pommier,
Mol. Cancer Ther. 2006, 5, 287; h) G. R. Pettit, V. Gad-
damidi, D. L. Herald, S. B. Singh, G. M. Cragg, J. M.
Schmidt, F. E. Boettner, M. Williams, Y. Sagawa, J.
Nat. Prod. 1986, 49, 995.
Adv. Synth. Catal. 2009, 351, 2702 – 2708
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2707

Zhiyuan Chen et al.
FULL PAPERS
Chem. 2003, 68, 6919; p) P. R. Carly, T. C. Govaerts,
S. L. Cappelle, F. Compernolle, G. J. Hoornaert, Tetra-
hedron 2001, 57, 4203; q) T. K. Sarkar, S. K. Ghosh,
T. J. Chow, J. Org. Chem. 2000, 65, 3111; r) P. R. Carly,
S. L. Cappelle, F. Compernolle, G. J. Hoornaert, Tetra-
hedron 1996, 52, 11889; s) J. A. R. Rodrigues, G. C.
Leiva, J. D. F. de Sousa, Tetrahedron Lett. 1995, 36, 59.
[13] a) H.-S. Yeom, J.-E. Lee, S. Shin, Angew. Chem. 2008,
120, 7148; Angew. Chem. Int. Ed. 2008, 47, 7040; b) H.-
S. Yeom, S. Kim, S. Shin, Synlett 2008, 924; c) Z. Huo,
H. Tomeba, Y. Yamamoto, Tetrahedron Lett. 2008, 49,
5531; d) Q. Ding, Z. Wang, J. Wu, Tetrahedron Lett.
2009, 50, 198.
[14] For recent reviews, see: a) L. El Kaim, L. Grimaud,
Tetrahedron 2009, 65, 2153; b) I. Akritopoulou-Zanze,
Curr. Opin. Chem. Biol. 2008, 12, 324; c) A. Dçmling,
Chem. Rev. 2006, 106, 17; d) A. Dçmling, I. Ugi,
Angew. Chem. 2000, 112, 3300; Angew. Chem. Int. Ed.
2000, 39, 3168. For recent selected examples, see: e) J.-
M. Grassot, G. Masson, J.-P. Zhu, Angew. Chem. 2008,
120, 961; Angew. Chem. Int. Ed. 2008, 47, 947; f) T.
Yue, M.-X. Wang, D.-X. Wang, J. Zhu, Angew. Chem.
2008, 120, 9596; Angew. Chem. Int. Ed. 2008, 47, 9454;
g) V. V. Tumanov, A. A. Tishkov, H. Mayr, Angew.
Chem. 2007, 119, 3633; Angew. Chem. Int. Ed. 2007, 46,
3563.
2708
asc.wiley-vch.de
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2702 – 2708