Enantioselective Arylation of 3-Carboxamide Oxindoles with Quinone Monoimines and Synthesis of Chiral Spirooxindole-benzofuranones

Article abstract of DOI:10.1055/s-0037-1611782

A highly enantioselective arylation of 3-carboxamide oxoindoles with quinone monoimines is described. Various 3-aryl-3-carboxamide oxindoles with an all-carbon quaternary center were obtained in moderate to good yields (up to 99%) with moderate to good enantioselectivities (up to 98%) in the presence of a bifunctional thiourea-tertiary amine catalyst. The absolute configuration of one product was determined by an X-ray crystal structural analysis and the absolute configurations of the other products can be assigned by analogy. Moreover, several chiral spirooxindole-benzofuranones were synthesized from the 3-aryl-3-carboxamide oxindoles in moderate yields with moderate to good enantioselectivities.

Full text of DOI:10.1055/s-0037-1611782

SYNLETT
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9
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© Georg Thieme Verlag Stuttgart · New York
2019, 30, A–F
letter
A
en
H. Chen et al.
Letter
Synlett
Enantioselective Arylation of 3-Carboxamide Oxindoles with
Quinone Monoimines and Synthesis of Chiral Spirooxindole-
benzofuranones
Hui Chena,b
Hui Liua,b
NHR5
R3
R4
O
CF3
NH
NR5
R3
Si-Han Zhaoa,b
Shao-Bing Chenga,b
Xiao-Ying Xua
Wei-Cheng Yuana
Xiao-Mei Zhang*a
HN
O
3i ( 2 mol% )
HO
S
R1
O +
R4
N
HN
O
O
CHCl3,–30 °C
N
R2
R1
N
N
CF3
H
H
N
R2
Bn
O
1
2
4
3i
0
0
0
0-0
0
0
2-0
9
0
2-1
6
5
5
23 examples
up to 99% yield
up to 98% ee
R1 = H, Alkyl, Halide
4 = H, Halide R5 = Sulfonyl
R2 = Alkyl R3 = Aryl, Alkyl
R
a Key Laboratory for Asymmetric Synthesis & Chirotech-
nology of Sichuan Province, Chengdu Institute of Organic
Chemistry, Chinese Academy of Sciences, Chengdu
610041, P. R. of China
xmzhang@cioc.ac.cn
b University of Chinese Academy of Sciences, Beijing,
100049, P. R. of China
Received: 08.02.2019
Accepted after revision: 17.03.2019
Published online: 02.04.2019
As excellent electrophilic reagents, quinone derivatives
have been widely used in asymmetric reactions to con-
struct structurally diverse chiral compounds.4i,4j,9,10 In re-
cent years, our group has also been engaged in research on
asymmetric reactions of quinone derivatives.4i,10n–p In a
continuation of our interest in this area, herein we describe
an enantioselective arylation of 3-carboxamide oxindoles
with quinone monoimines catalyzed by a bifunctional
thiourea-tertiary amine catalyst. This transformation en-
ables easy access to various novel 3-aryl-3,3-disubstituted
oxindoles in moderate to good yields (up to 99%) with mod-
erate to good enantioselectivities (up to 98%). In addition,
several chiral spirooxindole-benzofuranones were synthe-
sized from the 3-aryl-3-carboxamide oxindoles in moderate
yields with moderate to good enantioselectivities.
DOI: 10.1055/s-0037-1611782; Art ID: st-2019-l0077-l
Abstract A highly enantioselective arylation of 3-carboxamide oxo-
indoles with quinone monoimines is described. Various 3-aryl-3-carbox-
amide oxindoles with an all-carbon quaternary center were obtained in
moderate to good yields (up to 99%) with moderate to good enantiose-
lectivities (up to 98%) in the presence of a bifunctional thiourea-tertiary
amine catalyst. The absolute configuration of one product was deter-
mined by an X-ray crystal structural analysis and the absolute configu-
rations of the other products can be assigned by analogy. Moreover,
several chiral spirooxindole-benzofuranones were synthesized from the
3-aryl-3-carboxamide oxindoles in moderate yields with moderate to
good enantioselectivities.
Key words arylation, 3-carboxamide oxindoles, quinone monoimines,
3,3-disubstitutied oxindoles, spirooxindoles-benzofuranones
First, various chiral organocatalysts 3a–j were tested in
the arylation of 1-methyl-2-oxo-N-phenylindoline-3-car-
boxamide (3-amide oxindole) 1a with quinone monoimine
2a in dichloromethane at 0 °C. The results are summarized
in Scheme 1. All the catalysts exhibited good activity and
afforded the product with excellent yields in 10 minutes.
The two cinchona alkaloids 3a and 3b, and thiourea-tertia-
ry amine 3c provided the product with poor ee values.
When squaramide catalyst 3d was used, slightly better en-
antioselectivity was obtained. A selection of cinchona alka-
loids and L-amino acids incorporated in bifunctional
thiourea-tertiary amines 3e–h were then screened, in
which 3g delivered the best enantioselection (76% ee).
(1R,2R)-Cyclohexane-1,2-diamine and L-phenylalanine in-
corporated thiourea-tertiary amine 3i afforded the same ee
value as 3g. It is noteworthy that the racemic product was
obtained with the cinconidine and D-phenylalanine incor-
porated catalyst 3j, suggesting that the configuration of the
two parts of the catalyst must be matched to achieve high
3,3-Disubstitutied oxindoles, which are frequently
found in a variety of natural products and pharmaceutically
relevant compounds, have drawn much attention from both
synthetic and medicinal chemists.1 Among these com-
pounds, some 3-aryl-3,3-disubstituted oxindoles also ex-
hibit important physiological activities (Figure 1).2 Al-
though many strategies for the construction of chiral 3,3-
disubstituted oxoindoles have been established,3,4 there are
only a limited number of reports on the synthesis of chiral
3-aryl-3,3-disubstituted oxindoles.5–8 Generally, enantioen-
riched 3-aryl-3,3-disubstituted oxindoles are prepared by
asymmetric arylation of 3-monosubsituted oxindoles,5
asymmetric arylation of isatin derivatives,6 or asymmetric
functionalization of 3-aryl-oxindoles.7 Besides, Yuan and
co-workers demonstrated an indirect asymmetric hetero-
arylation of 3-substituted oxindoles through conjugated ad-
dition followed by Paal–Knorr cyclization.8
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

B
H. Chen et al.
Letter
Synlett
ble 1, entry 5). The reaction was then performed at lower
temperatures and clear increases in enantioselection were
observed (entries 8 and 9). A slightly higher ee value was
obtained when the reaction was performed in 2 mL of
chloroform (entry 10). To our delight, reducing the catalyst
loading to 5 and 2 mol% did not result in a decrease in enan-
tioselection (entries 11 and 12).
Cl
O
Cl
H3CO
CF
3 HO
H2N
N
O
N
H
O
Cl
NH2 HCl
anticancer reagent
Having established the optimal reaction conditions, the
scope of the reaction was examined. The results are sum-
marized in Table 2. First, a range of 3-carboxamide oxin-
doles bearing various substituents on the aromatic ring of
the amide were tested in the reaction with quinone monoi-
mine 2a. Generally, for 3-carboxamide oxindoles with para-
substituents on the N-phenyl group, the reactions proceed-
ed smoothly to afford the corresponding products in good
yields with good ee values (entries 2–6). Several substrates
with ortho-substituents on the N-phenyl group also provid-
ed the products in good yields with good ee values (entries
7–9). However, much lower enantioselectivity was obtained
with ortho-methoxy substrate 1j (entry 10). Two 3-carbox-
amide oxindoles with meta-substituents on the N-phenyl
group gave the products with good ee values but lower
yields (entries 11 and 12). N-Benzyl 3-carboxamide oxin-
dole 1m provided the product in moderate yield with mod-
erate ee value (entry 13), while N-cyclohexyl 3-carboxam-
ide oxindole 1n gave rise to excellent ee value but rather
SM-130686
OH
MeO
F
H3CO
N
Cl
Cl
O
N
N
O
O
SO2
N
H
F3C
OCH3
Flindokalner
H3CO
SSR-149415
Figure 1 Representative examples of biologically active 3-aryl-3,3-
disubstituted oxindoles
enantioselectivities. Hence 3i was determined as the opti-
mal catalyst for the reaction and used in the following in-
vestigations.
Subsequently, the other conditions were optimized.
First, various solvents were screened and chloroform was
found to be the most favorable solvent for the reaction (Ta-
NHTs
O
NHPh
O
NTs
Ph
HN
Cat* 3 ( 10 mol% )
HO
+
O
O
CH2Cl2, 0 °C
N
N
O
1a
4a
2a
O
N
N
N
H
H
H
OH
N
O
N
N
CF3
R
MeO
MeO
S
HN
CF3
CF3
N
N
N
3a: R = H, 99% yield, 30% ee
3b: R = H, 99% yield, 24% ee
3c: 99% yield, 7% ee
3d: 99% yield, 39% ee
CF3
CF3
CF3
CF3
N
R2
S
N
Bn
S
H
H
O
N
N
S
N
N
CF3
N
N
CF3
N
HN
H
H
H
H
R1
O
O
N
N
H
CF3
3e: R1 = OMe, R2 = i-Pr
H
Bn
99% yield, 28% ee
3f: R1 = OMe, R2 = t-Bu
99% yield, 28% ee
3g: R1 = OMe, R2 =Bn
99% yield, 76% ee
N
N
3i: 99% yield, 76% ee
3j: 99% yield, 0% ee
3h: R1 = H, R2 = Bn
99% yield, 70% ee
Scheme 1 Evaluation of the chiral catalysts in enantioselective arylation of 1-methyl-2-oxo-N-phenylindoline-3-carboxamide (1a) with quinone mono-
imine 2a. Unless otherwise specified, the reactions were carried out with 1a (0.10 mmol), 3a (0.12 mmol) and chiral catalyst 2 (0.01 mmol) in solvent
(1 mL) at 0 °C for 10 minutes. Isolated yield based on 1a. Enantiomeric excess was determined by HPLC analysis on a chiral stationary phase.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

C
H. Chen et al.
Letter
Synlett
Table 1 Optimization of the Conditionsa
Furthermore, a gram-scale reaction of 3-carboxamide
oxoindole 1a with quinone monoimine 2a was performed.
The reaction proceeded smoothly to give the product with-
out any loss in yield or enantioselection (Scheme 2).
NHTs
Ph
O
NHPh
NTs
HN
Cat* 3i
HO
O
+
O
O
Table 2 Enantioselective Arylation of 3-Carboxamide Oxindoles 1 with
Quinone Monoimine 2a
( 10 mol% )
N
N
O
1a
2a
4a
NHR5
R4
R3
Time (min.) Yield (%)b ee (%)c
O
NR5
Entry
Solvent
T (°C)
R3
NH
HN
HO
3i ( 2 mol% )
1
2
CH2Cl2
THF
0
0
10
10
10
10
10
10
10
30
60
60
60
60
99
99
99
99
95
99
99
88
82
80
80
80
76
75
9
+
R4
O
O
R1
O
R1
CHCl3, –30 °C
N
R2
N
R2
O
3
CH3CN
toluene
CHCl3
DCE
0
1
2
4
4
0
71
88
72
80
89
93
96
95
95
5
0
Entry
4
Yield (%)b ee (%)c
6
0
NHTs
R3
7
CHCl2CH2Cl
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
0
8
–10
–30
–30
–30
–30
HN
HO
1
4a: R3 = Ph
80
95
9
O
O
10d
11d,e
12d,f
N
2
3
4b: R3 = 4-FC6H4
4c: R3 = 4-ClC6H4
4d: R3 = 4-BrC6H4
4e: R3 = 4-MeC6H4
4f: R3 = 4-MeOC6H4
4g: R3 = 2-FC6H4
4h: R3 = 2-ClC6H4
4i: R3 = 2-MeC6H4
4j: R3 = 2-MeOC6H4
4k: R3 = 3-BrC6H4
4l: R3 = 3-MeOC6H4
4m: R3 = Bn
93
99
87
99
92
92
87
93
90
54
77
80
57
92
85
88
94
98
94
89
94
60
98
93
80
98
a Unless otherwise specified, the reactions were carried out with 1a (0.10
mmol), 2a (0.12 mmol) and chiral catalyst 3i (0.01 mmol) in solvent (1 mL).
b Yield of isolated product based on 1a.
4
c Enantiomeric excess was determined by HPLC analysis on a chiral station-
ary phase.
5
d The reaction was performed in CHCl3 (2 mL).
e 0.005 mmol of 3i was used.
6
f 0.002 mmol of 3i was used.
7
8
lower yield (entry 14). Moreover, 5-methyl-3-carboxamide
oxindole 1o was also investigated in the reaction with 2a
and moderate yield as well as moderate ee value was deliv-
ered (entry 15). 5-Chloro-3-carboxamide oxindole 1p re-
sulted in moderate yield but good enantioselectivity (entry
16). Excellent yields and excellent enantioselectivities were
obtained with 1-ethyl-3-carboxamide oxindole 1q (entry
17) and 1-allyl-3-carboxamide oxindole 1r (entry 18). Fi-
nally, some other quinone monoimines were subjected in
reaction with 3-carboxamide oxindole 1a. Changing the N-
substituent to Ns led to a considerable decrease in both
yield and enantioselection (entry 19). However, good yield
and good ee value were obtained with N-(4-methoxyben-
zene)sulfonyl quinone monoimine (entry 20). Reaction of
3-chloroquinone monoimine with 1a afforded the product
in good yield with moderate enantioselectivity (entry 21).
Unfortunately, changing the N-substituent of the quinone
monoimine to benzoyl led to an inseparable mixture (entry
22). Reaction of N-free 3-carboxamide oxindole 1s with
quinone monoimine 2a also failed to give the desired prod-
uct (entry 23).
9
10
11
12
13
14
4n: R3 = Cyclohexyl
NHTs
Ph
HN
HO
15
16
4o: R1 = Me
4p: R1 = Cl
75
75
73
92
R1
O
O
N
NHTs
Ph
HN
HO
17
4q
95
94
O
O
N
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

D
H. Chen et al.
Letter
Synlett
Table 2 (continued)
Entry
NHTs
O
4
Yield (%)b ee (%)c
NHPh
NTs
O
Ph
HN
Cat* 3i (2 mol%) HO
NHTs
O
+
O
O
CHCl3, –30 °C
N
Ph
HN
N
HO
18
4r
95
96
1a
2a
30 mmol
O
O
4a
25 mmol
1.16 g, 88 % yield
94 % ee
N
Scheme 2 Gram-scale reaction of 3-carboxamide oxindole 1a with qui-
none monoimine 2a
NHNs
Ph
HN
The absolute (S)-configuration of product 4q was deter-
mined by an X-ray crystal structural analysis (Figure 2).
Consequently, the absolute configurations of the other
products can be assigned by analogy.
HO
19
4s
63
84
O
O
N
MeO
NHTs
O
S
Ph
O
HN
NH
HO
O
O
20
4t
93
94
Ph
O
HN
N
HO
O
(S)-4q
N
NHTs
Ph
Figure 2 X-ray crystal structure of (S)-4q
Cl
HN
HO
21
22
23
4u
99
8
–
–
O
O
Although detailed structural and mechanistic studies
remain to be carried out, based on the absolute configura-
tion of the product 4q, we proposed a plausible transition-
state model for the reaction (Scheme 3).11 First, the 3-car-
boxamide oxindole is deprotonated by the bifunctional
thiourea-tertiary amine catalyst. The protonated tertiary
amine of the catalyst then activates the quinone monoi-
mine by H-bonding. Meanwhile, the thiourea moiety of the
catalyst is connected with the enolate generated by depro-
tonated 3-carboxamide oxindole through H-bonding. Final-
ly, the enolate attacks the quinone monoimine from the Si-face
followed by simultaneous aromatization to produce (S)-4q.
Spirooxindoles12 and spirobenzofuranones13 are privi-
leged scaffolds for drug development. Herein, we demon-
strated the utility of this methodology for easy access to
spirooxindole-benzofuranones. As can be seen in Scheme 4,
several 3-aryl 3,3-disubstituted oxindoles 4 were treated
with trifluoromethanesulfonic anhydride in the presence of
morpholine. Spirooxindole-benzofuranones 5a–c were pre-
pared in moderate yields without loss in enantioselection.
Surprisingly, the enantioselectivity of 5d cannot be re-
tained in the process of transformation. However, the rea-
son is still unclear.
N
NHBz
Ph
HN
HO
4v
N. D.
O
O
N
NHTs
Ph
HN
4w
N. D.
HO
O
O
N
H
a Unless otherwise specified, the reactions were carried out with 1 (0.10
mmol), 2 (0.12 mmol) and 3i (0.002 mmol) in CHCl3 (2 mL) at –30 °C for 1
hour.
b Isolated yield based on 1.
c The ee values were determined by using chiral HPLC.
d The absolute configuration of 4q was determined by an X-ray crystal
structural analysis and the absolute configurations of the other products
were assigned by analogy.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

E
H. Chen et al.
Letter
Synlett
Supporting Information
H
NHTs
Ph
N
O
Bn
N
N+
S
N
CF3
CF3
H
N
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1611782.
HN
Ts
S
u
p
p
orit
n
gInformati
o
n
S
u
p
p
orit
n
gInformati
o
n
HO
H
O
O
H
O-
N
O
N
References
O
HN
(S)-4q
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Scheme 3 Plausible reaction mechanism
NHTs
(2) (a) Tokunaga, T.; Hume, W. E.; Umezome, T.; Okazaki, K.; Ueki,
Y.; Kumagai, K.; Hourai, S.; Nagamine, J.; Seki, H.; Taiji, M.;
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TsHN
R1
Ph
HN
O
HO
morpholine
DCM, 0 °C
O
O
+
Tf2O
O
O
R1
N
R2
N
R2
5
4
(3) For reviews, see: (a) Cao, Z. Y.; Zhou, F.; Zhou, J. Acc. Chem. Res.
2018, 51, 1443. (b) Dalpozzo, R. Adv. Synth. Catal. 2017, 359,
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TsHN
TsHN
O
O
O
O
O
O
N
N
5a: 41% yield
5b: 40% yield
96% ee
73% ee
TsHN
TsHN
Cl
O
O
O
O
O
O
N
N
5c: 40% yield
5d: 50% yield
88% ee
80% ee
Scheme 4 Synthesis of spirooxindole-benzofuranones
In conclusion, we have developed an asymmetric aryla-
tion of 3-carboxamide oxindoles with quinone monoimines
catalyzed by a bifunctional thiourea-tertiary amine to con-
struct a series of chiral 3-aryl 3,3-disubstituted oxindoles in
moderate to good yields (up to 99%) with moderate to good
enantioselectivities (up to 98%).14,15 The absolute configura-
tion of one product was determined by an X-ray crystal
structural analysis and the absolute configurations of the
other products were assigned by analogy. Moreover, several
spirooxindole-benzofuranones were prepared from the
products in moderate yields with moderate to good enanti-
oselectivities.
(5) Jin, Y.; Chen, M.; Ge, S.; Hartwig, J. F. Org. Lett. 2017, 19, 1390.
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Funding Information
We are grateful for financial support from the National Natural Sci-
ence Foundation of China (21672208).
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6
7
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(14) Enantioselective Arylation of 2-Oxoindoline-3-carboxamide
1 with Quinone Monoimine 2; General Procedure: 2-Oxoin-
doline-3-carboxamide 1 (0.10 mmol) and catalyst 3i (0.002
mmol, 2 mol%) were dissolved in CHCl3 (2 mL) in a flame-dried
vial equipped with a magnetic stirring bar. After stirring for 30
minutes at –30 °C, quinone monoimine 2 (0.12 mmol, 1.2 equiv)
was added. The reaction mixture was stirred at –30 °C until no
starting material was detected by TLC. The mixture was sub-
jected to chromatography (silica gel, petroleum ether/EtOAc,
2:1) to afford the desired product 4.
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ChemistrySelect 2018, 3, 3975.
(15) 3-(2-Hydroxy-5-(4-methylphenylsulfonamido)phenyl)-1-
methyl-2-oxo-N-phenylindoline-3-carboxamide (4a): Yield:
0.042 g (80%); white solid; mp 169.0–171.5 °C; 95% ee, HPLC
condition: Chiralpak Ic-H (n-hexane/ethanol: 70:30, 1.0
20
mL/min, tmajor = 7.476 min, tminor = 9.122 min); []D = +25.2 (c
1.50, CH2Cl2). 1H NMR (300 MHz, DMSO-d6):  = 9.81 (s, 1 H),
9.67 (s, 1 H), 9.27 (s, 1 H), 7.55 (d, J = 8.0 Hz, 2 H), 7.45 (d, J =
7.9 Hz, 2 H), 7.33 (q, J = 7.5 Hz, 3 H), 7.19 (d, J = 7.9 Hz, 2 H),
7.16–6.98 (m, 4 H), 6.96–6.81 (m, 2 H), 6.58 (d, J = 8.5 Hz, 1 H),
3.22 (s, 3 H), 2.32 (s, 3 H). 13C NMR (100 MHz, DMSO-d6):  =
175.33, 164.48, 152.71, 143.96, 143.28, 138.39, 136.97, 129.79,
129.48, 129.16, 128.83, 128.63, 127.14, 126.56, 125.70, 124.54,
123.58, 122.94, 122.76, 120.51, 116.80, 108.88, 63.38, 27.13,
21.44. HRMS (ESI): m/z [M+Na]+ calcd. for C30H27N3O5SNa+:
550.1402; found: 550.1407.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F