Cascade One-Pot Synthesis of Indanone-Fused Cyclopentanes from the Reaction of Donor-Acceptor Cyclopropanes and Enynals via a Sequential Hydrolysis/Knoevenagel Condensation/[3+2] Cycloaddition

Article abstract of DOI:10.1002/adsc.201700345

A cascade reaction of donor-acceptor cyclopropanes with enynals to construct indanone-fused cyclopentanes via a sequential hydrolysis/Knoevenagel condensation/[3+2] cycloaddition is reported. The desired indanone-fused cyclopentanes were obtained in good yields. This method features mild reaction conditions and broad substrate scope, which render it very appealing to chemists for the synthesis of complex molecules containing an indanone-fused cyclopentane moiety. Moreover, the products could be further converted into compounds with different functional groups through the well-known transformations. (Figure presented.).

Full text of DOI:10.1002/adsc.201700345

Title: Cascade One-Pot Synthesis of Indanone-Fused Cyclopentanes
from the Reaction of Donor-Acceptor Cyclopropanes and Enynals
via a Sequential Hydrolysis/Knoevenagel Condensation/[3+2]
Cycloaddition
Authors: Shifa Zhu, Jiantao Zhang, and Huanfeng Jiang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700345
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Cascade One-Pot Synthesis of Indanone-Fused Cyclopentanes
from the Reaction of Donor-Acceptor Cyclopropanes and
Enynals
via
a
Sequential
Hydrolysis/Knoevenagel
Condensation/[3+2] Cycloaddition
Jiantao Zhang,a Huanfeng Jiang,a and Shifa Zhua,b*
a
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical
Engineering, South China University of Technology, Guangzhou, 510640, People’s Republic of China
Fax: (+86)-020-87111141; phone: (+86)-020-87111141; e-mail: zhusf@scut.edu.cn
b
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
Abstract:
A
cascade reaction of donor-acceptor
cyclopropanes with enynals to construct indanone-fused
cyclopentanes via a sequential hydrolysis/Knoevenagel
condensation/[3+2] cycloaddition was reported. The
desired indanone-fused cyclopentanes were obtained in
good yields. This method featured with mild reaction
conditions and broad substrate scope, which rendered it
very appealing to chemists for the synthesis of complex
molecules containing indanone-fused cyclopentanes
moiety. Moreover, the products could be further converted
into compounds with different functional groups through
the well-known transformations.
Figure 1. Representative Natural Products with All-
Carbon Tricyclic [6,5,5]-Fused Skeletons.
Keywords: Cascade reaction; Cycloaddition; Donor-
acceptor cyclopropane; Enynal; Cyclopentane;
On the other hand, donor-acceptor cyclopropanes
are well-known as 1,3-dipoles in cycloaddition
reactions.[9-11] For example, Tsuji reported the
addition reaction of vinylcyclopropane and methyl
vinyl ketone to yield the cyclopentane products as a
mixture of diastereomers.[11a] Trost and co-workers
have developed a palladium-catalyzed diastereo- and
enantioselective formal [3+2] cycloaddition reaction
between substituted vinylcyclopropanes and electron-
deficient olefins in the form of azlactone- and
Meldrum’s acid alkylidenes to give highly substituted
cyclopentane products[11b] (Scheme 1).
All-carbon polycyclic skeleton is an important
structural motif in a range of natural products and
pharmaceuticals. Among different types of all-carbon
polycyclic skeletons, tricyclic [6,5,5]-fused system is
a unique framework, and it is the core of many
important natural products, such as pallidol[1],
theacitrinin C[2] (Figure 1), dihydromaltophilin[3], and
paralianone C[4]. Therefore, efficient synthesis
methods for all-carbon tricyclic [6,5,5]-fused system
should be of great importance.[5]
Cascade reaction is a powerful synthetic strategy in
organic synthesis since it can introduce molecular
complexity through a simple chemical operation.[6] In
the past several years, our group has made a great
effort in developing efficient cascade reactions based
on enynals/enynones.[7,8] For example, we have
recently developed an efficient one-pot synthesis of
indanone-fused cyclobutenes[8a] and indanone-fused
2-methylene tetrahydrofurans[8b] from the reactions of
electron-deficient enynals with alkynes and propynols.
An in situ generated electron-deficient and high
reactive indenone was regarded as key intermediate
for these reactions.[8a-b]
Scheme
1.
Palladium-catalyzed
Annulation
of
Vinylcyclopropanes with Electron-deficient Olefins.
1
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
Table 1. Reaction Optimization between 1a and 2a.[a]
As part of our continuous efforts to develop new
cascade reactions based on enynals/enynones, we
envisioned that donor-acceptor cyclopropanes should
be used as efficient 1,3-dipoles to trap the in situ
generated electron-deficient indenones through [3+2]
cycloaddition reaction. Such reaction would allow a
facile synthesis of the all-carbon tricyclic [6,5,5]-
fused skeleton of indanone-fused cyclopentane
(Scheme 2).
entry cat
T/oC Yield[b] d.r.[c]
(%)
1
AgNTf2 (5 mol%)
60
60
60
n.d.
n.d.
n.d.
n.d.
n.d.
36
-
-
-
-
2
3
AgOTf (5 mol%)
AgSbF6 (5 mol%)
4
5
In(OTf)3 (20 mol%) 60
Fe(OTf)3 (20 mol%) 60
-
6[d]
7
ZnI2 (20 mol%)
ZnI2 (50 mol%)
ZnI2 (100 mol%)
ZnCl2 (50 mol%)
ZnBr2 (50 mol%)
ZnF2 (50 mol%)
Zn(OTf)2 (50 mol%) 60
ZnI2 (50 mol%)
ZnI2 (50 mol%)
60
60
60
60
60
60
67:33
80:20
71:29
77:23
73:27
-
69[e]
72
Scheme 2. Synthesis of Indanone-Fused Cyclopentanes.
8
9
Initial efforts have been made to investigate the
reaction of enynal 1a with donor-acceptor
cyclopropane 2a under different reaction conditions.
As shown in Table 1, AgNTf2, AgOTf, AgSbF6,
In(OTf)3, and Fe(OTf)3, which have been proven to
be good catalysts for the reaction of enynals,[8a-b]
however, were not able to promote this
transformation (Table 1, entries 1-5). Using 20 mol%
of ZnI2 as catalyst, the reaction could produce the
desired product cyclopentane 3a in 36% yield at 60
oC, with 12% of starting material 1a being recovered
(entry 6). Gratifyingly, when increasing the catalyst
amount to 50 mol%, the product yield of 3a was
improved to 69% (entry 7). Nevertheless, the yield
didn’t display an obvious improvement when 100
mol% ZnI2 was used instead (entry 8). ZnCl2 and
ZnBr2 were also effective for this reaction, but with
inferior results than ZnI2 (entries 9-10). ZnF2 and
Zn(OTf)2, however, were ineffective for the reaction
(entries 11-12). Trials to improve the product yields
by either reducing or raising the reaction temperature
failed (entries 13-14). The product yield remained
almost unchanged when 2.0 equivalents of 2a was
used, indicating that the reaction was insensitive to
the substrate ratio (entry 15). The reaction did not
occur when the 4Å molecular sieves were added to
remove the adventitious water introduced by solvent,
catalyst and substrate (entry 16). Furthermore, only
trace amount of 3a was detected when freshly dried
DCE was used as the solvent (entry 17). When 0.5
equivalent of H2O was added to the above reaction
mixture, the yield of product 3a can be improved to
72% (entry 18). Nevertheless, the yield can’t be
further improved by increasing the amount of water
(entries 19-20). These results implied that the
reaction should be a water-involved process. The
mixed solvents of DCE and MeOH failed to afford
the desired product (entry 21). It is noted that both
isomers of 3a have been observed for the ZnI2-
catalyzed reactions. The stereochemistry of the major
isomer, in which the ester group at C1 position and
the aryl group at C2 position oriented in the opposite
direction, has been determined by the X-ray
diffraction analysis (See 3f in SI for detail).[12]
32
43
NR
NR
51
56
67
NR
Trace
72
10
11
12
13
14
-
40
80
60
60
60
60
60
60
60
80:20
63:37
71:29
-
15[f] ZnI2 (50 mol%)
16[g] ZnI2 (50 mol%)
17[h] ZnI2 (50 mol%)
-
18[i]
ZnI2 (50 mol%)
ZnI2 (50 mol%)
78:22
79:21
82:18
-
19[j]
68
56
n.d.
20[k] ZnI2 (50 mol%)
21[l]
ZnI2 (50 mol%)
[a]
The reaction of 1a (0.20 mmol, 0.1M) and 2a (0.24
mmol), was carried out under N2 for 12h.
[b] The yield was determined by 1H NMR spectroscopy.
[c] d.r. was determined by 1H NMR spectroscopy.
[d] 12% of 1a was recovered.
[e] Yield of isolated products.
[f] 2.0 eq. of 2a was used.
[g] 4 Å M.S.(100 mg) was added.
[h]
Freshly dried DCE was used as the solvent.
[i] 0.5 eq. of H2O was added into the reaction system of
entry 17.
[j] 1.0 eq. H2O was added.
[k] 2.0 eq. H2O was added.
[l] DCE/MeOH (1:1) was used as the mixture solvent.
With the optimal reaction conditions in hand
(Table 1, entry 7), the substrate scope was then
investigated. As shown in Table 2, the cyclopropanes
bearing different aromatic substituents can be utilized
as effective substrates, affording the desired products
3a-k in 48-70% yields. The sterically-bulky aryl
groups had little effects on the product yields (3g-k).
Product 3c was not detected when dimethyl 2-(4-
methoxyphenyl)cyclopropane-1,1-dicarboxylate 2c
was used as the substrate, perhaps the catalyst was
poisoned by the coordination with the methoxy group
on 2c. In most cases, the electron-withdrawing group
at C1 position and the electron-donating group at C2
position of the major isomers are oriented in the
2
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
catalyst under N2 at 60 oC for 12 h; The yield is isolated
one; The d.r. refers to the ratio of diastereomer, and the
major isomer is the one where the EWG group at C1
position and the EDG group at C2 position oriented in
the opposite direction.
Table 2. Substrate Scope of Donor-Acceptor
Cyclopropanes with Enynals.[a]
[b]
[c]
The reaction of 1 (0.20 mmol), 2 (0.30 mmol) was
carried out at 40 oC for 12h;
The reaction of 1 (0.20 mmol), 2 (0.30 mmol) was
carried out at RT for 24h.
opposite directions. In the case of 3k, the ester group
(C1) and naphthyl group (C2) existing in the major
isomer are oriented in the same direction, which
might be attributed to the greater steric hindrance of
naphthyl group. It was found that the heteroaromatic
cyclopropanes were not tolerated in this reaction (3l-
m). In addition to aryl group, a vinyl group could also
be utilized as an electron-donating substituent for the
donor-acceptor cyclopropanes, affording the desired
product 3n in 71% yield. The substrate scope in
regards to enynals bearing different groups on the
alkyne or the benzene ring was further examined. As
expected, a series of desired vinyl-substituted
indanone-fused cyclopentanes (3n-z) can be obtained
in 32-86% yields. It is noteworthy that the reactions
with enynals bearing acyl group on the alkyne
displayed excellent diastereoselectivies (3t-z, d.r. >
99:1). The enynals with ester group on the alkyne
(3n-s, 59-86%) displayed better performances than
those with acyl group (3t-z, 32-54%). Furthermore,
the major diastereomer of 3n was also verified by the
X-ray diffraction analysis (See 3n in SI for detail).[13]
The reactions were unsuccessful for the enynals with
alkyoxy groups on the benzene ring (3aa-ab).
Besides, the enynal tethered with a heteroaryl was
also ineffective for the transformation (3ac). The
cyclopropane with an internal vinyl substituent was
not a suitable substrate (3ad). Replacing the donor-
acceptor cyclopropane with aziridine failed to give
the desired product either.[14]
The vinyl group of the indanone-fused
cyclopentanes 3n-z could be further converted into
different functional groups through the well-known
transformations. Taking 3n as an example (Scheme
3), the vinyl group can be coupled with iodobenzene
through Heck reaction[15], affording the desired
product 3ad in 63% yield (Scheme 3, eq. 1). In
addition to the cross coupling reaction, the vinyl
group of 3k could be reduced to ethyl group by Pd-
C/H2,[16] giving the desired product 4 in 72% yield
(eq. 2). Moreover, the vinyl group could be
selectively oxidized into an acyl group and expoxide
ring under Wacker oxidation[17] condition and in the
presence of m-CPBA as oxidant[18], respectively,
producing the corresponding products 5 and 6[19] in
good yields.
[a] The typical reaction of 1 (0.20 mmol, 0.1 M), 2 (0.24
mmol) was carried out using 50 mol% ZnI2 as the
3
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
Based on the previous reports for donor-acceptor
cyclopropanes[9-11] and our previous work on the
enynal chemistry,[8a-b] a plausible mechanism was
then proposed as shown in Scheme 5. An initial
activation of alkyne 1a through a [Zn]-π complex I
could produce the 5-exo-dig intermediate II,[20]
followed by a hydrolysis reaction, leading to the
formation of the ketone ester III in the presence of
adventitious and catalytic water. A sequential keto-
enol tautomerism/Knoevenagel condensation reaction
yielded the key intermediate indenone V and water
was released for the next hydrolysis reaction. On the
other hand, the 1,3-dipole A was generated in situ
from the ring-opening reaction of the donor-acceptor
cyclopropane 2 with the aid of zinc salt. Eventually, a
[3+2] cycloaddition reaction between the indenone V
and 1,3-dipole A occurred to furnish the desired
product 3.
Scheme 3. Synthetic Transformations of 3k.
To understand the role of the iodide, several
control experiments were conducted (Scheme 4).
Firstly, the reaction was completely depressed when
1.0 equivalent of Bu4NI was used as an additive
under the standard condition (Scheme 4, eq.1),
indicating that the free iodide (I-) ion might poison
the catalyst through the coordination with the metal
center. Secondly, the addition of 1.0 equivalent of KI
or NaI to the reaction has a negative effect on the
catalytic performance, the yields have been cut down
to 51% and 36%, respectively (eqs. 2-3). Thirdly,
instead of ZnI2, the combination of KI or NaI with
18-crown-6 can’t promote the reaction at all (eqs. 4-
5).
Scheme 5. Proposed Mechanism.
In summary, we have developed an efficient one-
pot approach to the synthesis of indanone-fused
cyclopentanes from the reaction of electron-deficient
enynals (1) and donor-acceptor cyclopropanes (2) via
a sequential hydrolysis/Knoevenagel condensation/
[3+2] cycloaddition. The desired indanone-fused
cyclopentanes were obtained in good yields. This
method featured with mild reaction conditions and
broad substrate scope, which is especially useful for
the synthesis of complex molecules containing
indanone-fused cyclopentanes moiety. Moreover, the
products could be further converted into compounds
with different functional groups through the well-
known transformations.
Scheme 4. Control Experiments for the Role of the Iodide.
4
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
[4] L. Wan, R. Chu, X. Peng, G. Zhu, M. Yu, L. Li, L.
Zhou, S. Lu, J. Dong, Z. Zhang, Y. Li, M. Qiu, J. Nat.
Prod. 2016, 79, 1628.
Experimental Section
General Procedure for Preparation of Aryl
cyclopropanes 2a-m. [21]
[5] a) C. L. Chandler, B. List, J. Am. Chem. Soc. 2008,
130, 6737. b) G. Lin, C. Li, S. Hung, R. Liu, Org. Lett.
2008, 10, 5059. c) C. J. Rieder, R. J. Fradette, F. G.
West, Chem. Commun. 2008, 1572. d) S. Rousseaux,
M. Davi, J. Sofack-Kreutzer, C. Pierre, C. E. Kefalidis,
E. Clot, K. Fagnou, O. Baudoin, J. Am. Chem. Soc.
2010, 132, 10706. e) L. Liu, L. Wei, Y. Lu, J. Zhang,
Chem. Eur. J. 2010, 16, 11813. f) Y. Cheng, J. Peng, Y.
Li, X. Shi, M. Tang, T. Tan, J. Org. Chem. 2011, 76,
1844. g) A. Schweinitz, A. Chtchemelinine, A.
Orellana, Org. Lett. 2011, 13, 232. h) K. Ambe-Suzuki,
Y. Ohyama, N. Shirai, S. Ikeda, Adv. Synth. Catal.
2012, 354, 879. i) M. M. Hansmann, M. Rudolph, F.
Rominger, A. S. K. Hashmi, Angew. Chem. 2013, 125,
2653; Angew. Chem. Int. Ed. 2013, 52, 2593. j) V. P.
Mehta, J. García-López, M. F. Greaney, Angew. Chem.
2014, 126, 1555; Angew. Chem. Int. Ed. 2014, 53,
1529. k) P. M. Holstein, M. Vogler, P. Larini, G. Pilet,
E. Clot, O. Baudoin, ACS Catal. 2015, 5, 4300. l) H. N.
Lim, G. Dong, Angew. Chem. 2015, 127, 15509;
Angew. Chem. Int. Ed. 2015, 54, 15294.
The cyclopropanes 2a-m were synthesized from the
corresponding aldehydes through a standard synthetic
sequence of Knoevenagel/Corey-Chaykovsky reactions.
General Procedure for Preparation of Dimethyl 2-
vinylcyclopropane-1,1-dicarboxylate 2n. [10d]
Dimethyl malonate (1.0 eq.) and 1, 4-dibromobut-2-ene
(1.0 eq.) were added to a round bottom flask with a stir bar
under an atmosphere of nitrogen. Tetrahydrofuran (0.2 M)
and cesium carbonate (2.5 eq.) were added afterwards. The
reaction mixture was then heated to 60 °C overnight. After
cooling down to room temperature, the reaction mixture
was filtered over celite and washed with diethyl ether. The
organic phase was washed with saturated aqueous
NaHCO3, followed by water and brine. After being dried
over MgSO4, the solvent was removed under reduced
pressure. The crude product was purified by means of
silica gel chromatography to give 2n.
[6] a) L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105,
137; Angew. Chem. Int. Ed. 1993, 32, 131. b) H.
Pellissier, Chem. Rev. 2013, 113, 442. c) L. F. Tietze,
Chem. Rev. 1996, 96, 115. d) S. E. Denmark, A.
Thorarensen, Chem. Rev. 1996, 96, 137. e) J. H. Kim,
Y. O. Ko, J. Bouffard, S. Lee, Chem. Soc. Rev. 2015,
44, 2489.
General methods for synthesis of indanone-fused
cyclopentanes 3.
To a solution of cyclopropane 2 in DCE was added ZnI2 at
room temperature and then the appropriate enynal 1. The
o
o
resulting reaction mixture was stirred at 40 C or 60 C
overnight. After completion of the reaction, the solvent
was removed under reduced pressure and the crude product
was subjected to silica gel column chromatography to
afford products 3.
[7] a) S. Zhu, Z. Zhang, X. Huang, H. Jiang, Z. Guo,
Chem. Eur. J. 2013, 19, 4695. b) S. Zhu, Z. Guo, Z.
Huang, H. Jiang, Chem. Eur. J. 2014, 20, 2425. c) S.
Zhu, L. Hu, H. Jiang, Org. Biomol. Chem. 2014, 12,
4104. d) S. Zhu, H. Huang, Z. Zhang, T. Ma, H. Jiang,
J. Org. Chem. 2014, 79, 6113. e) S. Zhu, X. Huang, T.
Zhao, T. Ma, H. Jiang, Org. Biomol. Chem. 2015, 13,
1225. f) J. Zhang, Y. Xiao, K. Chen, W. Wu, H. Jiang,
S. Zhu, Adv. Synth. Catal. 2016, 358, 2684.
Acknowledgements
[8] a) R. Liang, H. Jiang, S. Zhu, Chem. Commun. 2015,
51, 5530. b) R. Liang, K. Chen, Q. Zhang, J. Zhang, H.
Jiang, S. Zhu, Angew. Chem. 2016, 128, 2633 – 2637;
Angew. Chem. Int. Ed. 2016, 55, 2587. c) R. Liang, T.
Ma, S. Zhu, Org. Lett. 2014, 16, 4412.
We are grateful to Ministry of Science and Technology of the
People’s Republic of China (2016YFA0602900), the NSFC
(21372086, 21422204, and 21672071), Guangdong NSF
(2014A030313229, 2016A030310433), and the Fundamental
Research Funds for the Central Universities, SCUT. Prof. Li
Zhang from SYSU is specially acknowledged for her help in
language polishing.
[9] Selected reviews: a) H. Reissig, R. Zimmer, Chem. Rev.
2003, 103, 1151. b) D. Agrawal, V. K. Yadav, Chem.
Commun. 2008, 6471. c) C. A. Carson, M. A. Kerr,
Chem. Soc. Rev. 2009, 38, 3051. d) F. de Nanteuil, F.
De Simone, R. Frei, F. Benfatti, E. Serrano, J. Waser,
Chem. Commun. 2014, 50, 10912. e) M. A. Cavitt, L. H.
Phun, S. France, Chem. Soc. Rev. 2014, 43, 804. f) T. F.
Schneider, J. Kaschel, D. B. Werz, Angew. Chem. 2014,
126, 5608; Angew. Chem. Int. Ed. 2014, 53, 5504. g) I.
Kumar, RSC Adv. 2014, 4, 16397. h) S. Liao, X. Sun, Y.
Tang, Acc. Chem. Res. 2014, 47, 2260. i) H. K. Grover,
M. R. Emmett, M. A. Kerr, Org. Biomol. Chem. 2015,
13, 655.
References
[1] D. Mikulski, M. Molski, Eur. J. Med. Chem. 2010, 45,
2366.
[2] Y. Matsuo, K. Okuda, H. Morikawa, R. Oowatashi, Y.
Saito, T. Tanaka, J. Nat. Prod. 2016, 79, 189.
[3] P. R. Graupner, S. Thornburgh, J. T. Mathieson, E. L.
Chapin, G. M. Kemmitt, J. M. Brown, C. E. Snipes, J.
Antibiot. 1997, 50, 1014.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201700345
Advanced Synthesis & Catalysis
[10] a) S. Xing, Y. Li, Z. Li, C. Liu, J. Ren, Z. Wang,
Angew. Chem. 2011, 123, 12813; Angew. Chem. Int.
Ed. 2011, 50, 12605. b) B. M. Trost, P. J. Morris,
Angew. Chem. 2011, 123, 6291; Angew. Chem. Int.
Ed. 2011, 50, 6167. c) W. J. Humenny, P. Kyriacou,
K. Sapeta, A. Karadeolian, M. A. Kerr, Angew. Chem.
2012, 124, 11250; Angew. Chem. Int. Ed. 2012, 51,
11088. d) A. P. Dieskau, M. S. Holzwarth, B. Plietker,
J. Am. Chem. Soc. 2012, 134, 5048. e) X. Xia, X.
Song, X. Liu, Y. Liang, Chem. Asian J. 2012, 7, 1538.
f) Y. Zhou, J. Li, L. Ling, S. Liao, X. Sun, Y. Li, L.
Wang, Y. Tang, Angew. Chem. 2013, 125, 1492;
Angew. Chem. Int. Ed. 2013, 52, 1452. g) R. Tombe,
T. Kurahashi, S. Matsubara, Org. Lett. 2013, 15, 1791.
h) R. Tejero, A. Ponce, J. Adrio J. C. Carretero, Chem.
Commun. 2013, 49, 10406. i) S. Chakrabarty, I.
Chatterjee, B. Wibbeling, C. G. Daniliuc, A. Studer,
Angew. Chem. 2014, 126, 6074; Angew. Chem. Int.
Ed. 2014, 53, 5964. j) S. Racine, F. de Nanteuil, E.
Serrano, J. Waser, Angew. Chem. 2014, 126, 8624;
Angew. Chem. Int. Ed. 2014, 53, 8484. k) W. D.
Mackay, M. Fistikci, R. M. Carris, J. S. Johnson, Org.
Lett. 2014, 16, 1626. l) H. Xu, J. Hu, L. Wang, S.
Liao, Y. Tang, J. Am. Chem. Soc. 2015, 137, 8006. m)
W. Ma, J. Fang, J. Ren, Z. Wang, Org. Lett. 2015, 17,
4180. n) E. M. Budynina, O. A. Ivanova, A. O.
Chagarovskiy, Y. K. Grishin, I. V. Trushkov, M. Ya.
Melnikov, J. Org. Chem. 2015, 80, 12212. o) J.
Sabbatani, N. Maulide, Angew. Chem. 2016, 128,
6892; Angew. Chem. Int. Ed. 2016, 55, 6780. p) E.
Sanchez-Diez, D. L. Vesga, E. Reyes, U. Uria, L.
Carrillo, J. L. Vicario, Org. Lett. 2016, 18, 1270.
obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
[14] Replacing the donor-acceptor cyclopropane with
aziridine resulted into a complex system.
[15] G. Deng, H. Li, X. Yang, R. Song, M. Hu, J. Li, Org.
Lett. 2016, 18, 2012.
[16] X. Shen, R. Zhao, M. Mo, F. Peng, H. Zhang, Z.
Shao, J. Org. Chem. 2014, 79, 2473.
[17] S. Xing, Y. Li, Z. Li, C. Liu, J. Ren, Z. Wang, Angew.
Chem. 2011, 123, 12813; Angew. Chem. Int. Ed.
2011, 50, 12605.
[18] D. Lu, Y. Wan, L. Kong, G. Zhu, Chem. Commun.
2016, 52, 13971.
[19] CCDC 1526823 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
[20] a) N. Asao, T. Nogami, K. Takahashi, Y. Yamamoto,
J. Am. Chem. Soc. 2002, 124, 764; b) K. Miki, T.
Yokoi, F. Nishino, Y. Kato, Y. Washitake, K. Ohe, S.
Uemura, J. Org. Chem. 2004, 69, 1557; c) K. Miki, Y.
Washitake, K. Ohe, S. Uemura, Angew. Chem. 2004,
116, 1893; Angew. Chem. Int. Ed. 2004, 43, 1857. d)
R. Vicente, J. González, L. Riesgo, J. González, L. A.
López, Angew. Chem. 2012, 124, 8187; Angew.
Chem. Int. Ed. 2012, 51, 8063. e) J. González, J.
González, C. Pérez-Calleja, L. A. López, R. Vicente,
Angew. Chem. 2013, 125, 5965; Angew. Chem. Int.
Ed. 2013, 52, 5853. f) J. Ma, H. Jiang, S. Zhu, Org.
Lett. 2014, 16, 4472; g) S. Zhu, Q. Zhang, K. Chen, H.
Jiang, Angew. Chem. 2015, 127, 9546; Angew. Chem.
Int. Ed. 2015, 54, 9414. h) D. Zhu, J. Ma, K. Luo, H.
Fu, L. Zhang, S. Zhu, Angew. Chem. 2016, 128, 8592;
Angew. Chem. Int. Ed. 2016, 55, 8452. i) H. Luo, K.
Chen, H. Jiang, S. Zhu, Org. Lett. 2016, 18, 5208.
[11] a) I. Shimizu, Y. Ohashi, J. Tsuji, Tetrahedron Lett.
1982, 23, 3825. b) B. M. Trost, P. J. Morris, S. J.
Sprague, J. Am. Chem. Soc. 2012, 134, 17823. c) A. P.
Dieskau, M. S. Holzwarth, B. Plietker. J. Am. Chem.
Soc. 2012, 134, 5048. d) M. Laugeois, S. Ponra, V.
Ratovelomanana-Vidal, V. Michelet, M. R. Vitale,
Chem. Commun. 2016, 52, 5332.
[12] CCDC 1524932 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
[21] H. Zhang, Y. Luo, H. Wang, W. Chen, P. Xu, Org.
Lett. 2014, 16, 4896.
[13] CCDC 1524933 contains the supplementary
crystallographic data for this paper. These data can be
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10.1002/adsc.201700345
Advanced Synthesis & Catalysis
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7
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