Selective construction of polycyclic spirooxindoles: Via a Cu(OTf)2/HOTf-catalyzed domino reaction of o -arylalkynylacetophenones and 3-phenacylideneoxindoles

Article abstract of DOI:10.1039/c7ob01292f

Under the combined catalysis of Cu(OTf)₂/HOTf, the domino annulation reaction of o-arylalkynyl acetophenones with 3-phenacylideneoxindoles in refluxing acetonitrile selectively afforded functionalized spiro[indoline-3,7′-tetrapheno[7,6-bc]furan

Full text of DOI:10.1039/c7ob01292f

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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Selective Construction of Polycyclic Spirooxindoles via
Cu(OTf)2/HOTf-catalyzed Domino Reaction of o-
Arylalkynylacetophenones and 3-Phenacylideneoxindoles
Received 00th January 20xx,
Accepted 00th January 20xx
Ren-Yin Yanga, Jing Suna*, Qiu Suna, and Chao-Guo Yana*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Under the combined catalysis of Cu(OTf)2/HOTf, the domino As
a member of the family of o-alkynylarylcarbonyl
annulation reaction of o-arylalkynyl acetophenones with 3- compounds, 2-alkynylarylketones also attract great interest
phenacylideneoxindoles in refluxing acetonitrile selectively from many chemists. The Lewis/Bronsted acid induced
afforded
functionalized
spiro[indoline-3,7'-tetrapheno[7,6- intramolecular electrophilic cyclization of 2-alkynylarylketones
bc]furans]
and spiro[indeno[1,2-b]naphtho[2,1-d]furan-7,3'- has proven to be a versatile synthetic approach to a variety of
indolines] depending on electron effect of the substituents on biologically interesting heterocycles and carbocycles. In
both substrates.
general, the known cyclization processes of o-
alkynylarylketones undergoing through isobenzofuranium
intermediates are limited to simple nucleophilic additions,
which exclusively lead to isobenzofuran derivatives (Scheme 1,
path a).,8 Alternately, the same isobenzopyrylium intermediate
with o-alkynylarylketones, undergoes a cycloaddition with an
alkene/alkyne moiety to generate polycyclic compounds
(Scheme 1, path b).9 Besides the two major reaction pathways,
it is also known that o-alkynylarylketones preferentially
undergo C-5-exo-dig cyclizations to form carbopalladation
intermediates (Scheme 1, path c),10 and undergo a C-6-endo-
dig cyclizations to form the powerful intermediate
naphthalenol (Scheme 1, path d),11 but the domino reaction
starting from this pathway has been no reported yet. A
literature survey indicated that the synthesis of
spirooxindoline derivatives using the o-alkynylarylketones still
not been reported.
Spirooxindolines are an important class of naturally occurring
substances characterized by their important bioactivity and
interesting structural properties.1,2 Recently, these powerful
units have emerged as interesting target compounds for
synthesis because of their biological activities, which include
cholinesterase inhibition,3a anticancer,3b antibacterial,3b and
anti-inflammatory activities.3c Thus, many methods have been
developed for the synthesis of compounds with these scaffolds
as core structures.4 In recent decades, o-alkynylarylcarbonyl
series and their derivatives have been widely studied and
utilized as versatile building blocks in organic synthesis5,
because these species undergo many transformations,
containing nucleophilic addition reactions6 and Diels–Alder
cycloaddition reactions7.
3-Phenacylideneoxindoles act as effective precursors for the
synthesis of biologically important spirooxindole compounds12
and have attracted much attention, including that of our
group.13 Various nucleophilic reactants have been shown to
proceed smoothly with this interesting reaction unit.13 Thus,
the reaction diversity of the cycloaddition of the o-
alkynylarylketones with 3-phenacylideneoxindoles led us to
examine the reactivity of analogues of these two substrates.
Herein, we report the multi-step cycloaddition reaction of the
Scheme 1. Intramolecular Cyclization Reactions of o-Alkynylarylketones
o-alkynylarylketones and 3-phenacylideneoxindoles via
a
Cu(OTf)2/HOTf catalytic system for the efficient synthesis of
complex spirooxindoline derivatives. The diversity of products
controlled by the electronic properties of the reactants was
systematically studied.
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Table 1. Reaction Optimization for the Synthesis of 3aa
mol% HOTf and 5 mol% Cu(OTf)2 was employed in the reaction,
the yield of product 3a significantly increased to 81% (entry
11). The Cu(OTf)2/HOTf catalyst in other solvents, such as
toluene, THF, acetonitrile and CH2Cl2, also resulted in complex
mixtures (entries 12-15). Prolonging the reaction time to 24 h
led to an 82% yield (entry 16), and the reaction was not
successful at room temperature. The reaction was only result
in 49% yield under N2 atmosphere. On the basis of these
results, we found that the optimized reaction conditions for
the domino reaction were the combination of Cu(OTf)2/HOTf
as a catalyst in refluxing DCE for approximately 12 h under air
condition.
Entry
Catalysts (mol %)
HOTf (5)
Solvent
Yield (%) b
1
2
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
Tol
N.D.
N.D.
N.D.
N.D.
N.D.
trace
46
With the optimized reaction conditions (Table 1, entry 14)
in hand, we examined the substrate scope. The results are
summarized in Table 2. o-(Phenylethynyl)acetophenone and its
4-methyl- and 4-methoxy-substituted derivatives reacted
smoothly with various 2-phenacylideneoxindolines to give the
.
InCl3 4H2O (5)
3
In(OTf)3 (5)
Cu(OTf)2 (5)
Cu(ClO4)2 (5)
4
5
expected spiro[indoline-3,7′-tetrapheno[7,6-bc]furans] 3a-3p
.
6
BF3 Et2O (5)
in 61-91% yields (Table 2, entries 1-16), On these case, the
substituents on 3-phenacylideneoxindoles showed marginal
7
In(OTf)3 (5) + HOTf (10)
.
8
InCl3 4H2O (5) + HOTf (10)
45
effect
on
the
reaction.
When
o-(4-
fluorophenylethynyl)acetophenone was used in the reaction,
the reaction afforded the expected spiro compound 3q in only
16% yield (Table 2, Entries 17). Another unexpected
spiro[indeno[1,2-b]naphtho[2,1-d]furan-7,3′-indoline] 4q was
obtained in 36% yield, which was clearly produced from the
sequential annulation reaction of the phenyl group of the 3-
phenacylidene moiety with the carbon atom at the 3-position
of the oxindoline. Additionally, the yield of product 3r was too
low to isolate, and the cyclopentyl spirooxindole 4r was
obtained in 43% yield (Table 2, entry 18). Similarly, the o-(4-
chlorophenylethynyl)acetophenone also resulted in the
cyclopentyl spirooxindoles 4s and 4t in moderate yields (Table
9
Cu(OTf)2 (5) + HOTf (10)
Cu(ClO4)2 (5) + HOTf (10)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
Cu(OTf)2 (5) + HOTf (20)
47
10
11
12
13
14
15
16c
17d
18e
trace
81
trace
trace
trace
trace
82
THF
CH3CN
CH2Cl2
DCE
DCE
DCE
trace
49
2, entries 19-20). However, both substrate
1 and substrate 2
a reaction conditions unless otherwise stated: 1a o-(alkynyl)arylketone (0.5
mmol, 0.110 g), 2a 3-phenacylideneoxidole (0.5 mmol, 0.177 g), solvent (10
bearing p-chloro groups resulted in a complex mixture of
products, from which the cyclohexyl spirooxindole 3u was
separated out in 5% yield (Table 2, entry 21). The substrates
bearing electron-withdrawing p-nitro groups predominately
gave the corresponding spiro[indeno[1,2-b]naphtho[2,1-
d]furan-7,3′-indoline] 4t-4x in 55-66% yields (Table 2, entries
22-24), whereas the normal spiro compounds 3t-3x were not
obtained from the reaction system. These results clearly
c
mL), reflux, 12 h reaction time, ND = not detected; b Isolated yield; 24 h
e
d
reaction time; Reaction at room temperature; Reaction under N2
atmosphere.
Initially,
o-phenylethynylacetophenone
(1a
)
and
3-
phenacylideneoxindole (2a) were chosen as the substrates for
the model reaction. Various catalysts and solvents were
examined (Table 1). HOTf and different Lewis acids in refluxing
1,2-dichloroethane (DCE) were found to be inefficient for this
Table 2 Substrate scope a
.
transformation (entries 1-5). When BF3 Et2O was used as a
catalyst in refluxing DCE, similar results were afforded (entry
6). When In(OTf)3 and HOTf were combined as catalysts in
refluxing DCE, the polycyclic spirooxindoline 3a was formed in
moderate yields (entry 7). Its molecular structure was assigned
as the functionalized spiro[indoline-3,7′-tetrapheno[7,6-
bc]furan] by spectroscopic methods. To improve the reaction,
.
a combination of InCl3 4H2O, Cu(OTf)2, and Cu(ClO4)2/HOTf was
tested in different ratios as a catalyst. The combination of 5
mol% of In(OTf)3 or Cu(OTf)2 with 10 mol% of HOTf gave the
product 3a in 45-47% yield (entries 8-9); however, Cu(ClO4)2 in
refluxing DCE was still inefficient for this transformation, even
with 10 mol% HOTf (Entry 10). When the combination of 20
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atmosphere. The further intramolecular Friedel–Crafts
alkylation depended on the properties of the two aryl groups
Entry
1
R1
H
R2
H
R3
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
nꢀBu
Bn
Bn
Bn
Bn
Bn
Bn
Bn
nꢀBu
R4
CH3
Cl
Compd (Yield, %) b
R1 and R4 in the intermediate ( ). When R1 = H, p-CH3, or p-
G
3a (81)
3b (84)
3c (80)
3d (76)
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
2
H
H
OCH3, the FC alkylation reaction of the carbon atom at the 3-
position of the oxindoline moiety on the activated aryl group
3
R1 resulted in the cyclohexyl spirooxindole . When R1 = p-F, p-
3
H
Cl
Cl
CH3
H
Cl
4
H
CH3
Cl, or p-NO2, the aryl ring connecting R1 was deactivated and
the FC alkylation on it was obviously inhibited. An alternative
FC alkylation of the aryl group R4 gave the cyclopentyl
5
H
OCH3 3e (76)
6
H
NO2
H
3f (90)
3g (91)
3h (82)
3i (87)
3j (79)
3k (83)
3l (64)
3m (77)
3n (80)
3o (74)
4.
When both R1 and R4 were electron-
7
H
Cl
H
spirooxindole
8
CH3
CH3
CH3
OCH3
OCH3
OCH3
OCH3
CH3
Cl
ꢀ
withdrawing chloro or nitro groups, the FC alkylations on both
of the deactivated aryl rings were suppressed. Thus, the
reaction resulted in a mixture of products, from which the
9
H
ꢀ
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Cl
H
Cl
ꢀ
intermediate of naphtho[1,2-b]furan (G) was separated as a
CH3
CH3
Cl
ꢀ
stable product.
Cl
Cl
F
ꢀ
To shed some light on the proposed reaction mechanism,
some control experiments were carried out. Firstly, the
reaction of proposed intermediate 3-(p-tolyl)naphthalen-1-ol
ꢀ
CH3
H
ꢀ
(
D1) with 3-(p-nitrophenacylidene)oxindoline 2a resulted in
OCH3 CH3
ꢀ
polycyclic spirooxindoline 3h in 78% yield, which strongly
supported the mechanism proceeding through the reaction
between naphthalenol and 3-phenacylideneoxindoles (eq. 1 in
OCH3
F
Cl
H
OCH3 3p (61)
ꢀ
CH3
CH3
3q (16)
4q (36)
4r (43)
4s (51)
4t (62)
F
F
ꢀ
Scheme
2).
Secondly,
the
reaction
of
with
o-(4-
3-(p-
chlorophenylethynyl)acetophenone
1f
Cl
H
CH3
ꢀ
nitrophenacylidene)oxindoline 2b resulted in naphtho[1,2-
b]furan (F1) in only 6% yield, which also showed that the
electron-withdrawing groups on both aryl groups strongly
prevented the sequential FC alkylation reaction (eq. 2 in
Scheme 2). The single-crystal structures of compound (F1) was
also determined by X-ray diffraction. Notably, Peddinti’s group
Cl
CH3
CH3
H
OCH3
Cl
ꢀ
Cl
3u (5)
NO2
NO2
NO2
CH3
ꢀ
ꢀ
ꢀ
4v (59)
4w (66)
4x (55)
CH3
Cl
OCH3
OCH3
recently reported
a BF3·OEt2-mediated cyclization of β-
a reaction conditions: 3-phenacylideneoxidole (0.5 mmol), o-(alkynyl)arylketone
(0.5 mmol), HOTf (0.1 mmol, 0.015 g), Cu(OTf)2 (0.025 mmol, 0.090 g) in DCE (10
mL), reflux, 12 hrs; under air condition b Isolated yield.
naphthol with 3-phenacylideneoxindoles to give the
benzofuran derivatives without the sequential annulation
reaction,15 which certifies the formation of 3-aryl-1-
naphthalenol (D) in our reaction.
indicate that the electronic effect of the substituents not only
affected the yields of the products, but also determined the
reaction pathways. The structures of the spiro compounds 3a-
3u and 4q-4x were fully characterized by IR, HRMS, and 1H and
13C NMR spectroscopy. The single-crystal structures of the
seven spiro compounds 3h (Figure 1), 3j, 3k, 3m, 4q (Figure 1),
4r, and 4v were successfully determined by X-ray diffraction.
On the basis of the aforementioned experimental results
4
and previously reported similar works,
a plausible
mechanism was proposed, as shown in Scheme 1. Firstly, an
enol intermediate ( ) was formed in the presence of stronger
3h
4q
A
acid HOTf. Then, under the catalysis of Cu(OTf)2, the
Figure. 1 Molecular structure of spiro compound 3h and 4q
coordination of Cu2+ to the C-C triple bond increased its
electrophilic reactivity, which is drawn in intermediate (B).
Thus, intermediate (C) was formed in the presence of the
strong acid HOTf and strong Lewis acid Cu(OTf)2, which in
turn converted to the naphthalenol (D) by isomerization.11a In
the presence of the catalyst Cu(OTf)2, the addition of
naphthalenol (
adduct ( ). The acid-catalyzed intramolecular dehydration of
the adduct ( ) afforded a naphtho[1,2-b]furan ( ), and the
oxidation of (F) was easily occurred at tertiary carbon position
D) to 3-phenacylideneoxindole 2 produced an
E
E
F
afforded corresponding 3-hydroxyoxindole
(G) under air
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1
Experimental procedures, analytical data, and copies of the H
and 13C NMR spectra, HRMS spectra for all new products (3a-
3s and 4o-4v, 6a, G1) (PDF). Single-crystal X-ray data for 3h
(CCDC 1523295), 3j (CCDC 1523296), 3k (CCDC 1523297), 3m
(CCDC 1523298), 4q (CCDC 1523299), 4r (CCDC 1523300), 4v
(CCDC 1523301), G1 (CCDC 1526533).
Notes and references
We are grateful to the National Natural Science Foundation of
China (No. 21172189 and 21572196) and the Priority Academic
Program Development of Jiangsu Higher Education Institutions
for financial support (No. BK2013016). The Analytical Center of
Yangzhou University is acknowledged for the analytical
assistance.
1
For selected reviews of spirooxindoline, see: (a) M. A.
Koch, A. Schuffenhauer, M. Scheck, S. Wetzel, M.
Casaulta, A. Odermatt, P. Ertl and H. Waldmann, Proc.
Natl. Acad. Sci. U. S. A. 2005, 102, 17272–17277. (b) H.Lin
and S. J. Angew. Chem., Int. Ed. 2003, 42, 36–51. (c) C.
V.Galliford, and K. A. Scheidt, Angew. Chem., Int. Ed. 2007,
46, 8748–8758. (d) F. Zhou, Y. L. Liu and J. Zhou Adv.
Synth. Catal. 2010, 352, 1381–1407. (e) N. R. Ball-Jones, J.
J. Badillo and A. K. Franz Org. Biomol. Chem. 2012, 10
,
5165–5181. (f) G. S. Singh and Z. Y. Desta, Chem. Rev.
2012, 112, 6104–6155. (g) L. Hong and R. Wang, Adv.
Synth. Catal. 2013, 355, 1023–1052. (h) M. M. M. antos
Tetrahedron 2014, 70, 9735-9757. (i) B. Yu, D.-Q. Yu and
H.-M Liu, Eur. J. Med. Chem. 2015, 97, 673-698. (j) N. Ye, H.
Chen, E. A. Wold, P.-Y. Shi and J. Zhou ACS Infect. Dis.
Scheme 2 Plausible reaction mechanism for domino reaction
2016,
For examples, see: (a) A. Ashimori, B. Bachand, L. E.
Overman and D. J. Poon, J. Am. Chem. Soc. 1998, 120
2, 382-392.
2
,
6477–6487. (b) P. R. Sebahar and R. M. Williams, J. Am.
Chem. Soc. 2000, 122, 5666–5667. (c) C. Marti and E. M.
Carreira, Eur. J. Org. Chem. 2003, 2003, 2209–2219. (d)
R.Tripathy, A. Reiboldt, P. A. Messina, M. Iqbal, J. Singh, E.
R. Bacon, T. S. Angeles, S. X. Yang, M. S. Albom, C.
Robinson, H. Chang, B. A. Ruggeri and J. P. Mallamo,
Bioorg. Med. Chem. Lett. 2006, 16, 2158–2162. (e) R.
Murugan, S. Anbazhagan and S. S. Narayanan, Eur. J. Med.
Chem. 2009, 44, 3272–3279. (f) B. K. Yeung, B. Zou, M.
Rottmann, S. B. Lakshminarayana, S. H. Ang, S. Y. Leong, J.
Tan, J. Wong, S. Keller-Maerki, C. Fischli, A. Goh, E. K.
Schmitt, P. Krastel, E. Francotte, K. Kuhen, D. Plouffe, K.
Henson, T. Wagner, E. A. Winzeler, F. Petersen, R. Brun, V.
Dartois, T. T. Diagana and T. H. Keller, J. Med. Chem. 2010,
53, 5155–5164. (g) G. Kumari, Nutan, M. Modi, S. K. Gupta
and R. K. Singh, Eur. J. Med. Chem. 2011, 46, 1181–1188.
(h) S. l. Patir and Ertürk, E. J. Org. Chem. 2011, 76, 335–
338. (i) E. Busto, V. Gotor-Fernandez and V. Gotor, J. Org.
Chem. 2012, 77, 4842–4848. (j) K. Guo, T. Fang, J. Wang,
A. A. Wu, Y. Wang, J. Jiang, X. Wu, S. Song, W. Su and Q.
Xu, Bioorg. Med. Chem. Lett. 2014, 24, 4995–4998. (k) Y.
Feng, M. M. Majireck and S. M. Weinreb, J. Org. Chem.
2014, 79, 7–24.
Scheme 3 Control Experiments
Conclusions
In summary, we systematically investigated Cu(OTf)2/HOTf-
catalyzed domino reactions of o-(alkynyl)aryl ketones with 3-
phenacylideneoxindoles and found very interesting reaction
outcomes depending on the structures of the substrates. The
reaction mechanism was clearly elucidated by the isolation of
reaction intermediates and some control experiments. This
domino reaction not only provided an efficient method for the
syntheses of functionalized spiro[indoline-3,7
′-tetrapheno[7,6-
3
For examples of biologically important spirooxindolines,
see: (a) Y. Kia, H. Osman, R. S. Kumar, V. Murugaiyah, A.
Basiri, S. Perumal, H. A. Wahab and C. S. Bing, Bioorg.
Med. Chem. 2013, 21, 1696–1707. (b) Y. Arun, G. Bhaskar,
C. Balachandran, S. Ignacimuthu and P. Perumal, Bioorg.
Med. Chem. Lett. 2013, 23, 1839–1845. (c) J. Qu, L. Fang,
X. D. Ren, Y. Liu, S. S. Yu, L. Li, X. Q. Bao, D. Zhang, Y. Li and
S. G. Ma, J. Nat. Prod. 2013, 76, 2203–2209.
bc]furans] and spiro[indeno[1,2-b]naphtho[2,1-d]furan-7,3
′-
indolines], but also established the practical application of the
domino C–C coupling reaction in organic synthesis. Further
studies on the domino coupling reactions for the synthesis of
polycyclic systems are in progress.
Supporting Information
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4
For examples, see: (a) G. Schäfer and J. W. Bode, Angew.
Chem., Int. Ed. 2011, 50 10913–10916. (b) R. T.
Naganaboina and R. K. Peddinti, J. Org. Chem. 2013, 78
12819–12824. (c) K. Mori, M. Wakazawa and T. Akiyama,
Chem. Sci. 2014, , 1799–1803. (d) Y. Q. Wang, Z. S. Wei,
C. Q. Zhu, Y. Y. Ren and C. Wu, Tetrahedron 2016, 72
4643–4654.
(b) M. Bai, Y. You, Y. Z. Chen, G. Y. Xiang, X. Y. Xu, X. M.
Zhang, W. C. Yuan, Org. Biomol. Chem., 2016, 14, 1395–
1401.
15 N. Sharma and R. K. Peddinti, J. Org. Chem. 2017, 82, 918–
924.
,
,
5
,
5 For selected very recent examples of applications of o-
alkynylbenzcarbonyl, see (a) U. Kloeckner, P. Finkbeiner
and B. J. Nachtsheim, J. Org. Chem. 2013, 78, 2751–2756.
(b) S. Manojveer and R. Balamurugan, Org. Lett. 2014, 16
,
1712–1715. (c) V. Reddy, A. S. Jadhav and R. V. Anand,
Org. Biomol. Chem. 2015, 13, 3732–3741 (d) W. Z. Zhang,
M. W. Yang, X. T. Yang, L. L. Shi, H. B. Wang and X. Lu, B.
Org. Chem. Front. 2016, 3, 217–221. (e) Y. N. Wu, R. Fu, N.
N. Wang, W. J. Hao, G. Li, S. J. Tu and B. Jiang, J. Org.
Chem. 2016, 81, 4762–4770. (f) B. Guo and R. Hua,
Tetrahedron 2016, 72, 4608–4615. (g) M. Zhang, W. Ruan,
H. J. Zhang, W. Li and T. B. Wen, J. Org. Chem. 2016, 81
1696–1703.
,
6 J. Barluenga, H. Vázquez-Villa, A. Ballesteros and J. M.
Gonzàlez, J. Am. Chem. Soc. 2003, 125, 9028–9029. (a) S.
Zhu, Z. Guo, Z. Huang and H. Jiang, Chem. –Eur. J. 2014,
20, 2425–2430.
7 (a) N. Asao, K. Takahashi, S. Lee, T. Kasahara and Y.
Yamamoto, J. Am. Chem. Soc. 2002, 124, 12650–12651.
(b) N. Asao, T. Kasahara and Y. Yamamoto, Angew. Chem.,
Int. Ed. 2003, 42, 3504–3506. (c) N. Asao, T. Nogami, S.
Lee and Y. Yamamoto, J. Am. Chem. Soc. 2003, 125
,
10921–10925. (d) Z. L. Hu, W. J. Qian, S. Wang, S. Wang
and Z. J. Yao, J. Org. Chem. 2009, 74, 8787–8793. (e) Z. L.
Hu, W. J. Qian, S. Wang, S. Wang and and Z. Yao J. Org.
Lett. 2009, 11, 4676–4679. (f) S. Zhu, L. Hu and H. Jiang,
Org. Biomol. Chem. 2014, 12, 4104–4111. (g) L. Mo, L. L.
Wu, S. Wang and Z. J. Yao, Org. Lett. 2015, 17, 3314–3317.
M. E. Domaradzki, Y. Long, Z. She, X. Liu, G. Zhang and Y.
Chen, J. Org. Chem. 2015, 80, 11360–11368.
8
9
(a) S. Zhu, H. Huang, Z. Zhang, T. Ma and H. Jiang, J. Org.
Chem. 2014, 79, 6113–6122. (b) B. Guo, Y. Zhou, L. Zhang
and R. Hua, J. Org. Chem. 2015, 80, 7635–7641.
10 N. Chernyak, S. I. Gorelsky and V. Gevorgyan, Angew.
Chem., Int. Ed. 2011, 50, 2342–2345.
11 (a) M. A. Ciufolini and T. J. Weiss, Tetrahedron Lett. 1994,
35, 1127–1130. (b) S. P. Shukla, R. Tiwari and A. K. Verma,
Tetrahedron 2012, 68, 9035–9044.
12 For examples, see: (a) G. Bencivenni, L. Y. Wu, A.
Mazzanti, B. Giannichi, F. Pesciaioli, M. P. Song, G. Bartoli
and P. Melchiorre, Angew. Chem., Int. Ed. 2009, 48, 7200–
7203. (b) B. Tan, N. Candeias and C. Barbas III, Nat. Chem.
2011, 3, 473–477. (c) B. Tan, G. Hernández-Torres and C.
F. Barbas III, J. Am. Chem. Soc. 2011, 133, 12354–12357.
(d) G. Wang, X. Liu, T. Huang, Y. Kuang, L. Lin and X. Feng,
Org. Lett. 2013, 15, 76–79. (e) S. Xu, C. Li, X. Jia and J. Li, J.
Org. Chem. 2014, 79, 11161–11169.
13 For recent examples, see: (a) J. Sun, Y. Sun, H. Gong, Y. J.
Xie and C. G. Yan, Org. Lett. 2012, 14, 5172–5175. (b) J.
Sun, Y. J. Xie and C. G. Yan, J. Org. Chem. 2013, 78, 8354–
8365. (c) H. Gong, J. Sun and C. G. Yan, Tetrahedron 2014,
70, 6641–6650. (d) H. Gong, J. Sun and C. G. Yan, Synthesis
2014, 46, 2327–2332. (e) J. Zhang, H. Gao, J. Sun and C. G.
Yan, Eur. J. Org. Chem. 2014, 5598–5602. (f) J. Sun, L.
Chen, H. Gong and C. G. Yan, Org. Biomol. Chem. 2015, 13
5905–5917. (g) F. Yang, J. Sun, H. Gao and C. G. Yan, RSC
Adv. 2015, , 32786–32794. (h) G. L. Shen, J. Sun and C. G.
,
5
Yan, Org. Biomol. Chem. 2015, 13, 10929–10938.
14 (a) D. Sano, K. Nagata, T. Itoh, Org. Lett, 2008, 10, 1593-
1595.
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Selective Construction of Polycyclic Spirooxindoles via Cu(OTf)2/HOTf-catalyzed Domino
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