Organocatalytic Enantioselective Decarboxylative Michael Addition of β-Keto Acids to Dicyanoolefins and Disulfonylolefins

Article abstract of DOI:10.1002/adsc.201600485

A convenient organocatalytic enantioselective decarboxylative Michael addition of β-keto acids to dicyanoolefins and disulfonylolefins is realized. In the presence of saccharide-derived chiral amino thioureas, the reaction proceeded smoothly to afford a wide range of the Michael adducts in 62–99% yield with 70–94% ee. Moreover, one of the chiral adducts obtained could be readily converted into the monofluorinated product in a total 68% yield over four steps with 85% ee. (Figure presented.).

Full text of DOI:10.1002/adsc.201600485

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DOI: 10.1002/adsc.201600485
Organocatalytic Enantioselective Decarboxylative Michael Addi-
tion of b-Keto Acids to Dicyanoolefins and Disulfonylolefins
Yi Wei,a Ran Guo,a Yanfeng Dang,a Jing Nie,a and Jun-An Maa,b,*
a
Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, and
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, Peopleꢀs Republic of
China
Fax : (+86)-22-2740-3475; e-mail: majun_an68@tju.edu.cn
State Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300072, Peopleꢀs Republic of China
b
Received: May 7, 2016; Revised: June 5, 2016; Published online: && &&, 0000
Abstract: A convenient organocatalytic enantiose-
lective decarboxylative Michael addition of b-keto
acids to dicyanoolefins and disulfonylolefins is real-
ized. In the presence of saccharide-derived chiral
amino thioureas, the reaction proceeded smoothly
to afford a wide range of the Michael adducts in
62–99% yield with 70–94% ee. Moreover, one of
the chiral adducts obtained could be readily con-
verted into the monofluorinated product in a total
68% yield over four steps with 85% ee.
alysts (Scheme 1c). Herein, we report the results of
our exploration on this subject.
We initiated our studies by evaluating the enantio-
selective decarboxylative Michael addition of 3-oxo-3-
phenylpropanoic acid 1a to 2-benzylidenemalononi-
trile 2a (Table 1) in tetrahydrofuran (THF) at 08C
using the saccharide-derived amino thioureas I–VI,
which were developed previously in our laboratory,[10]
as chiral catalysts. Under these reaction conditions,
the Michael addition product 3a was obtained in ex-
cellent yield (Table 1, entries 1–6), with catalyst III
giving the best enantioselectivity (51% ee). Subse-
quently, the solvent was found to have an important
effect on the asymmetric induction (entries 7–10).
Among the solvents tested, toluene was found to be
the solvent of choice for this decarboxylative Michael
addition with respect to both the yield and stereose-
lectivity (entry 9). When the reaction was performed
Keywords: amino thioureas; decarboxylative Mi-
chael addition; enantioselectivity; b-keto acids; or-
ganocatalysis
Since the Michael addition reaction[1] is arguably one at a lower temperature (entries 11 and 12), the enan-
of the most powerful organic transformations avail- tioselectivity was improved from 73% ee at 08C to
able for the construction of useful multifunctional 88% ee at À208C. In addition, the stereoinduction
molecules,[2] the development of efficient catalytic
enantioselective approaches to this reaction has been
an attractive subject in chemical research.[3] b-Keto
acids are promising nucleophilic candidates for the
generation of ketone enolate equivalents under very
mild reaction conditions,[4] and recent studies have led
to the rapid development of catalytic enantioselective
decarboxylative reactions of b-keto acids with various
electrophilic partners.[5,6] The asymmetric Michael ad-
dition reactions of b-keto acids to nitroolefins and
a,b-unsaturated ketones have been approached using
chiral metal complexes and small organic molecule
catalysts by the groups of Evans[7a] and Kim[7b,c]
(Scheme 1a and b). Encouraged by these results and
the fact that dicyanoolefins[8] and disulfonylolefins[9]
are highly reactive Michael acceptors, recently we
have developed a new organocatalytic enantioselec-
tive decarboxylative Michael addition of b-keto acids
to dicyanoolefins and disulfonylolefins that uses the
readily accessible amino thioureas as bifunctional cat- of b-keto acids.
Scheme 1. Catalytic asymmetric Michael addition reactions
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Table 1. Catalyst screening and optimization of the reaction conditions.[a]
Entry
Catalyst (mol%)
Solvent
Temp. [oC]
Time [h]
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
I (10)
THF
THF
THF
THF
THF
THF
Et2O
DCM
toluene
CH3CN
toluene
toluene
toluene
toluene
0
0
0
0
0
0
0
0
0
0
À20
À30
À20
À20
48
48
48
48
48
48
60
60
60
60
96
120
96
96
95
93
98
97
94
97
98
96
98
90
98
83
98
98
0
8
II (10)
III (10)
IV (10)
V (10)
VI (10)
III (10)
III (10)
III (10)
III (10)
III (10)
III (10)
III (15)
III (20)
51
48
5
24
60
58
73
0
88
86
85
88
9
10
11
12
13
14
[a]
General reaction conditions: 1a (0.24 mmol), 2a (0.2 mmol), and catalyst I–VI in solvent (2.0 mL) at the given tempera-
ture for the stated time.
Yields of isolated product averaged over two runs.
[b]
[c]
Determined by HPLC analysis on a chiral stationary phase. The absolute stereochemistry was assigned by comparison of
the optical rotation with reported literature data (ref.[8e]).
was not improved when the catalyst loading was in- (entry 15). Further exploration of the substrate scope
creased to 15 or 20 mol% (entries 13 and 14). focused on the Michael acceptors. The introduction of
With the optimized conditions in hand, we turned electron-donating and electron-withdrawing groups
our focus to the substrate scope and generality of this on the phenyl ring of 2-benzylidenemalononitrile had
decarboxylative Michael addition reaction. The re- little influence on the enantioselectivity. The desired
sults are summarized in Table 2. First, a large variety products 3p–3w were obtained in high yields with
of b-keto acids were examined for their reactions with good enantioselectivities (entries 16–23). An acceptor
2-benzylidenemalononitrile 2a. In the presence of substrate with a heteroaromatic group also reacted,
10 mol% catalyst III, the reaction of ortho-, meta-, affording the corresponding Michael adduct 3x in
and para-substituted phenyl b-keto acids with 2a all 96% yield with 76% ee (entry 24). The use of alkyl-
proceeded smoothly, thus generating the Michael substituted dicyanoolefins furnished the expected
products 3a–3k in high yields (88–98%) with good products 3y and 3z in moderate yields and enantiose-
enantioselectivities (82–94% ee) (entries 1–11). lectivities (entries 25 and 26).
Fused-ring aryl- or heteroaryl-substituted b-keto acids
To further extend this asymmetric decarboxylative
could also be used as the Michael donors, thus deliv- Michael addition protocol, we also used a series of di-
ering the corresponding adducts 3l–3n in 90–96% sulfonylolefins as the Michael acceptors under the
yield and 82–86% ee (entries 12–14). An alkyl-substi- current reaction conditions. As shown in Table 3, all
tuted b-keto acid is also a viable substrate, affording of the Michael adducts 5a–5o were obtained with
the desired product 3o in 99% yield with 64% ee good to high enantioselectivities (80–93% ee) (en-
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Table 2. The decarboxylative 1,4-addition of 2-benzylidenemalononitrile 2a with various b-keto acids.[a]
Entry
R/R’ (3)
Time [h]
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
C6H5/C6H5 (3a)
96
96
96
144
96
98
93
95
97
98
93
88
96
92
91
97
90
96
90
99
84
80
90
90
92
98
98
98
96
60
65
88
86
86
87
85
84
94
84
86
84
82
86
82
85
64
82
80
82
88
86
82
87
87
76
70
78
2-MeC6H4/C6H5 (3b)
3-MeC6H4/C6H5 (3c)
2,4-Me2C6H3/C6H5 (3d)
4-MeOC6H4/C6H5 (3e)
3-MeOC6H4/C6H5 (3f)
4-FC6H4/C6H5 (3g)
2-FC6H4/C6H5 (3h)
4-ClC6H4/C6H5 (3i)
3-ClC6H4/C6H5 (3j)
4-BrC6H4/C6H5 (3k)
1-naphthyl/C6H5 (3l)
2-naphthyl/C6H5 (3m)
3-thiophenyl/C6H5 (3n)
cyclopropyl/C6H5 (3o)
C6H5/4-MeC6H4 (3p)
C6H5/4-MeOC6H4 (3q)
C6H5/3-PhOC6H4 (3r)
C6H5/4-FC6H4 (3s)
144
144
144
144
96
120
144
144
144
20
144
144
144
144
144
48
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
C6H5/4-ClC6H4 (3t)
C6H5/3,4-Cl2C6H3 (3u)
C6H5/4-BrC6H4 (3v)
C6H5/3-NO2C6H4 (3w)
C6H5/3-pyridyl (3x)
C6H5/n-propyl (3y)
C6H5/i-propyl (3z)
72
72
72
72
72
[a]
General reaction conditions: 1 (0.24 mmol), 2 (0.2 mmol), and catalyst III (10 mol%) in toluene (2.0 mL) at À208C for
the stated time.
Yields of isolated product averaged over two runs.
[b]
[c]
Determined by HPLC analysis on a chiral stationary phase.
tries 1–15), yet the chemical yields were dependent on 6 in 92% yield with 87% ee. After the reduction of
the position and electronic properties of the substitu- the carbonyl group of 6 with NaBH4, the correspond-
ents on the aromatic rings of the substrates. For ex- ing alcohol 7 was subjected to reductive desulfonyla-
ample, b-keto acids that contain an electron-with- tion and PCC oxidation to afford monofluorinated
drawing group on the phenyl ring delivered the de- ketone 8 in 78% yield with 85% ee (Scheme 2). The
sired products 5f and 5g in relatively lower yields (en- absolute configuration of the major enantiomer was
tries 6 and 7), whereas disulfonylolefins that bear an assigned by comparison of the optical rotation with
electron-donating group on the phenyl ring reacted the reported literature data.[12]
slowly with b-keto acids, furnishing the corresponding
To explain the predominant production of adducts
adducts 5k and 5l in 72% yield after prolonged reac- and to shed some light on the mechanism, the M06-
tion times (entries 11 and 12). However, alkyl-substi- 2X DFT calculations[13,14] were performed with a view
tuted b-keto acids and dicyanoolefins were found to of delineating the interactions between organocatalyst
be unsuitable for this asymmetric transformation and and substrates (see the Supporting Information). The
no expected product was observed.
preliminary results show that the thiourea moiety of
Notably, the presence of the sulfonyl moiety within the organocatalyst favorably bonds to one trans-nitro-
the Michael adducts allows facile access to optically gen atom of dicyanoolefins and one cis-oxygen atom
enriched fluorine-containing building blocks.[11] For of disulfonylolefins, respectively (Figure 1a). The mul-
À
example, simple treatment of the decarboxylative Mi- tiple H O bonding interactions between the saccha-
chael adduct 5a with the Selectfluor under basic con- ride unit of the organocatalyst and the olefin sub-
ditions led to the formation of the fluorinated ketone strate may also play an important role in stabilizing
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Table 3. The decarboxylative 1,4-dddition of b-keto acids 1 to vinyl sulfones 4.[a]
Entry
R/R’’ (5)
Time [h]
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
C6H5/C6H5 (5a)
48
96
96
96
96
48
48
96
96
96
144
144
24
48
72
98
99
94
92
93
62
80
95
74
90
72
72
99
75
99
90
89
92
80
93
88
90
89
87
87
85
84
87
86
80
4-MeC6H4/C6H5 (5b)
2,4-Me2C6H3/C6H5 (5c)
4-MeOC6H4/C6H5 (5d)
3-MeOC6H4/C6H5 (5e)
4-FC6H4/C6H5 (5f)
4-ClC6H4/C6H5 (5g)
1-naphthyl/C6H5 (5h)
2-naphthyl/C6H5 (5i)
3-thiophenyl/C6H5 (5j)
C6H5/4-MeC6H4 (5k)
C6H5/4-MeOC6H4 (5l)
C6H5/4-FC6H4 (5m)
C6H5/4-ClC6H4 (5n)
C6H5/2-naphthyl (5o)
9
10
11
12
13
14
15
[a]
General reaction conditions: 1 (0.24 mmol), 4 (0.2 mmol), and catalyst III (10 mol%) in toluene (2.0 mL) at 08C for the
stated time.
[b]
[c]
Yields of isolated product averaged over two runs.
Determined by HPLC analysis on a chiral stationary phase.
the transition state. In addition, the b-keto acid is de- proached by the enol to give the observed major S
protonated by the tertiary amine moiety of the orga- enantiomer of 3, whereas the attack of the enol to the
nocatalyst. After deprotonation, the enol species asso- si-face of the C=C group of disulfonylolefins leads to
ciates closely with the catalyst through ionic interac- the formation of the S-configured adduct 5. In addi-
tions. From the above analysis and the absolute con- tion, the catalytic cycle could involve a stepwise pro-
figurations of the adducts, the transition states (TS-A cess, in which the Michael addition of b-keto acids to
and TS-B) for the Michael addition of b-keto acid olefins gave the addition intermediates, followed by
1 to olefins (2 and 4) in the presence of chiral organo- the decarboxylation to afford the desired adducts.
catalyst III are proposed in Figure 1b. The re-face of
In summary, a new organocatalytic enantioselective
the C=C group of dicyanoolefins is predominantly ap- decarboxylative Michael addition of b-keto acids to
dicyanoolefins and disulfonylolefins has been present-
ed. In the presence of the saccharide-derived chiral
amino thioureas, the reaction proceeded smoothly to
afford a wide range of the Michael adducts in 62–
99% yield with 70–94% ee. Moreover, the products
obtained can be converted into optically active mono-
fluorinated molecules. Further mechanistic investiga-
tions and additional applications to the synthesis of
biologically interesting targets are underway in our
laboratory.
Experimental Section
General Procedure for Enantioselective
Decarboxylative Michael Addition of b-Keto Acids to
Dicyanoolefins
Scheme 2. Further synthetic transformations of the Michael
adduct 5a.
The 2-benzylidenemalononitrile 2 (0.2 mmol), catalyst III
(0.02 mmol) and b-keto acid 1 (0.24 mmol) in toluene
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Figure 1. (a) Intermolecular complexes between organocatalyst and olefins (N blue, O red, S yellow). (b) Proposed reaction
pathway.
(2.0 mL) were added into a 10-mL Schlenk flask equipped References
with a stirring bar. The reaction mixture was then stirred at
À208C. After completion of the reaction (monitored by
TLC), the residue was purified by column chromatography
on silica gel (eluting with 5:1 petroleum ether/ethyl acetate)
to give the addition product 3.
[1] a) A. Michael, J. Prakt. Chem. 1887, 35, 349; b) A. Mi-
chael, Am. Chem. J. 1887, 9, 115; c) A. Michael, J.
Prakt. Chem. 1894, 49, 20.
[2] a) V. J. Lee, in: Comprehensive Organic Synthesis, Vol.
4, (Eds.: B. M Trost, I. Fleming), Oxford, 1991, Chap-
ters 1.2, 1.3, 1.4; b) P. Perlmutter, in: Conjugate Addi-
tion Reactions in Organic Synthesis, Oxford, 1992;
c) R. D. Little, M. R. Masjedizadeh, O. Wallquist, J. I.
McLoughlin, Org. React. 1995, 47, 315; d) J. Christoff-
ers, G. Koripelly, A. Rosiak, M. Rçssle, Synthesis 2007,
1279; e) T. Tokoroyama, Eur. J. Org. Chem. 2010, 10,
2009; f) W.-Q. Chen, J.-A. Ma, in: Comprehensive Or-
ganic Synthesis, Vol. 4, (Eds.: P. Knochel, G. A. Mo-
lander), Oxford, Elsevier 2014, Chapter 4.01.
[3] For recent reviews of catalytic enantioselective Michael
additions, see: a) A. Alexakis, C. Benhaim, Eur. J. Org.-
Chem. 2002, 3221; b) J. Christoffers, A. Baro, Angew.
Chem. 2003, 115, 1726; Angew. Chem. Int. Ed. 2003, 42,
1688; c) D. Almasi, D. A. Alonso, C. Nꢂjera, Tetrahe-
dron: Asymmetry 2007, 18, 299; d) T. Thaler, P. Kno-
chel, Angew. Chem. 2009, 121, 655; Angew. Chem. Int.
Ed. 2009, 48, 645; e) T. Jerphagnon, M. G. Pizzuti, A. J.
Minnaard, B. L. Feringa, Chem. Soc. Rev. 2009, 38,
1039; f) J. L. Vicario, E. Reyes, L. Carrillo, U. Uria, in:
Comprehensive Organic Synthesis, Vol. 4, (Eds.: P. Kno-
chel, G. A. Molander), Oxford, Elsevier 2014, Chapter
4.03.
General Procedure for the Decarboxylative Michael
Addition of b-Keto Acids to Disulfonylolefins
The disulfonylolefin 4 (0.2 mmol), catalyst III (0.02 mmol)
and b-keto acid 1 (0.24 mmol) in toluene (2.0 mL) were
added into a 10-mL Schlenk flask equipped with a stirring
bar. The reaction was then stirred at 08C. After completion
of the reaction (monitored by TLC), the residue was puri-
fied by column chromatography on silica gel (eluting with
3:1 petroleum ether/ethyl acetate) to give the addition prod-
uct 5.
Acknowledgements
This work was supported financially by the National Natural
Science Foundation of China (No. 21225208, 21472137, and
21532008), the National Basic Research Program of China
(973 Program: 2014CB745100 and 2015CB856500), and
Tianjin Municipal Science
& Technology Commission
(14JCQNJC06200). The authors also thank Professor Zhi-
Xiang Wang (University of the Chinese Academy of Scien-
ces) for his helpful discussions and suggestions.
[4] For recent reviews, see: a) Y. Pan, C.-H. Tan, Synthesis
2011, 2044; b) L. Bernardi, M. Fochi, M. C. Franchini,
Adv. Synth. Catal. 0000, 000, 0 – 0
5
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A. Ricci, Org. Biomol. Chem. 2012, 10, 2911; c) Z.-L.
Wang, Adv. Synth. Catal. 2013, 355, 2745; d) S. Naka-
mura, Org. Biomol. Chem. 2014, 12, 394.
Khiar, Tetrahedron 2000, 56, 3749; c) S. Kojima, K. Fu-
jitomo, Y. Itoh, K. Hiroike, M. Murakami, K. Ohkata,
Heterocycles 2006, 67, 679; d) S. Kojima, M. Suzuki, A.
Watanabe, K. Ohkata, Tetrahedron Lett. 2006, 47, 9061;
e) L. Yue, W. Du, Y.-K. Liu, Y.-C. Chen, Tetrahedron
Lett. 2008, 49, 3881; f) H.-L. Cui, Y.-C. Chen, Chem.-
Commun. 2009, 447.
[5] For recent examples from Maꢀs group, see: a) X.-J. Li,
H.-Y. Xiong, M.-Q. Hua, J. Nie, Y. Zheng, J.-A. Ma,
Tetrahedron Lett. 2012, 53, 2117; b) Y. Zheng, H.-Y.
Xiong, J. Nie, M.-Q. Hua, J.-A. Ma, Chem. Commun.
2012, 48, 4308; c) H.-N. Yuan, S. Wang, J. Nie, W.
Meng, Q. Yao, J.-A. Ma, Angew. Chem. 2013, 125,
3961; Angew. Chem. Int. Ed. 2013, 52, 3869; d) H.-Y.
Xiong, Z.-Y. Yang, Z. Chen, J.-L. Zeng, J. Nie, J.-A.
Ma, Chem. Eur. J. 2014, 20, 8325; e) H.-X. Zhang, J.
Nie, H. Cai, J.-A. Ma, Org. Lett. 2014, 16, 2542; f) X.-
D. Tang, S. Li, R. Guo, J. Nie, J.-A. Ma, Org. Lett.
2015, 17, 1389; g) B.-N. Lai, J.-F. Qiu, H.-X. Zhang, J.
Nie, J.-A. Ma, Org. Lett. 2016, 18, 520.
[6] For recent examples from other groups, see: a) K.
Rohr, R. Mahrwald, Org. Lett. 2011, 13, 1878; b) C.-F.
Yang, C. Shen, J.-R. Wang, S.-K. Tian, Org. Lett. 2012,
14, 3092; c) F. Zhong, W. Yao, X. Dou, Y. Lu, Org.
Lett. 2012, 14, 4018; d) C. Jiang, F. Zhong, Y. Lu, Beil-
stein J. Org. Chem. 2012, 8, 1279; e) J. Zuo, Y.-H. Liao,
X.-M. Zhang, W.-C. Yuan, J. Org. Chem. 2012, 77,
11325; f) C. W. Suh, C. W. Chang, K. W. Choi, Y. J.
Lim, D. Y. Kim, Tetrahedron Lett. 2013, 54, 3651; g) Z.
Duan, J. Han, P. Qian, Z. Zhang, Y. Wang, Y. Pan, Org.
Biomol. Chem. 2013, 11, 6456; h) Z. Duan, J. Han, P.
Qian, Z. Zhang, Y. Wang, Y. Pan, Beilstein J. Org.
Chem. 2014, 10, 969; i) F.-L. Zhu, Y.-H. Wang, D.-Y.
Zhang, X.-H. Hu, S. Chen, C.-J. Hou, J. Xu, X.-P. Hua,
Adv. Synth. Catal. 2014, 356, 3231.
[9] a) Q. Zhu, Y. Lu, Org. Lett. 2008, 10, 4803; b) A.
Landa, M. Maestro, C. Masdeu, . Puente, S. Vera, M.
Oiarbide, C. Palomo, Chem. Eur. J. 2009, 15, 1562;
c) X. Dou, Y. Lu, Org. Biomol. Chem. 2013, 11, 5217;
d) B. Qiao, Q. Liu, H. Liu, L. Yan, Z. Jiang, Chem.
Asian J. 2014, 9, 1252.
[10] a) K. Liu, H.-F. Cui, J. Nie, K.-Y. Dong, X.-J. Li, J.-A.
Ma, Org. Lett. 2007, 9, 923; b) H. Ma, K. Liu, F.-G.
Zhang, C.-L. Zhu, J. Nie, J.-A. Ma, J. Org. Chem. 2010,
75, 1402; c) H.-N. Yuan, S. Li, J. Nie, Y. Zheng, J.-A.
Ma, Chem. Eur. J. 2013, 19, 15856.
[11] a) P. Kirsch, in: Modern Fluoroorganic Chemistry: Syn-
thesis Reactivity, Applications, Wiley-VCH, Weinheim,
2004; b) J.-A. Ma, D. Cahard, Chem. Rev. 2008, 108,
PR1; c) C. Ni, M. Hu, J. Hu, Chem. Rev. 2015, 115, 765;
d) X. Yang, T. Wu, R. J. Phipps, F. D. Toste, Chem. Rev.
2015, 115, 826.
[12] T. Furukawa, N. Shibata, S. Mizuta, S. Nakamura, T.
Toru, M. Shiro, Angew. Chem. 2008, 120, 8171; Angew.
Chem. Int. Ed. 2008, 47, 8051.
[13] a) Y. Zhao, D. G. Truhlar, Theor. Chem. Acc. 2008, 120,
215; b) Y. Zhao, D. G. Truhlar, Acc. Chem. Res. 2008,
41, 157.
[14] a) Y. Zhao, D. G. Truhlar, J. Chem. Theory Comput.
2009, 5, 324; b) A. V. Marenich, C. J. Cramer, D. G.
Truhlar, J. Phys. Chem. B 2009, 113, 6378; c) A. D. Kul-
karni, D. G. Truhlar, J. Chem. Theory Comput. 2011, 7,
2325.
[7] a) D. A. Evans, S. Mito, D. Seidel, J. Am. Chem. Soc.
2007, 129, 11583; b) H. W. Moon, D. Y. Kim, Tetrahe-
dron Lett. 2012, 53, 6569; c) Y. K. Kang, H. J. Lee,
H. W. Moon, D. Y. Kim, RSC Adv. 2013, 3, 1332.
[8] a) J. L. Marco, J. Org. Chem. 1997, 62, 6575; b) I.
Fernꢂndez, C. S. Araffljo, M. J. Romero, F. Alcudia, N.
Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers!

COMMUNICATIONS
Organocatalytic Enantioselective Decarboxylative Michael
Addition of b-Keto Acids to Dicyanoolefins and
Disulfonylolefins
7
Adv. Synth. Catal. 2016, 358, 1 – 7
Yi Wei, Ran Guo, Yanfeng Dang, Jing Nie, Jun-An Ma*
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!