Facile synthesis of optically active oxindoles by copper-catalyzed asymmetric monotosylation of prochiral 1,3-diols

Article abstract of DOI:10.1016/j.tetasy.2010.03.015

A facile synthetic method toward optically active 3,3-disubstituted oxindoles with excellent enantioselectivity was achieved using chiral copper-catalyzed desymmetrization of prochiral 1,3-diols. The monotosylated product was transformed into oxindole derivatives efficiently.

Full text of DOI:10.1016/j.tetasy.2010.03.015

Tetrahedron: Asymmetry 21 (2010) 1370–1373
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Facile synthesis of optically active oxindoles by copper-catalyzed asymmetric
monotosylation of prochiral 1,3-diols
*
Masami Kuriyama, Satoko Tanigawa, Yuki Kubo, Yosuke Demizu, Osamu Onomura
Graduate School of Biomedical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852-8521, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A facile synthetic method toward optically active 3,3-disubstituted oxindoles with excellent enantiose-
lectivity was achieved using chiral copper-catalyzed desymmetrization of prochiral 1,3-diols. The mono-
tosylated product was transformed into oxindole derivatives efficiently.
Received 1 March 2010
Accepted 11 March 2010
Available online 13 April 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Dedicated to Professor Henri Kagan on the
occasion of his 80th birthday
1. Introduction
benzyloxindole 1e led to a moderate yield while keeping 99% ee,
N-(p-methylbenzyl)oxindole 1f decreased both the chemical yield
Oxindols are important heterocycles found in various natu-
rally occurring compounds and biologically active molecules.1
In particular, numerous methods have been reported for the
enantioselective synthesis of oxindoles including Heck reaction,2
cyanoamidation,3 cycloaddition,4 alkylation,5 arylation,6 1,2-addi-
tion,7 1,4-addition,8 hydroxylation,9 fluorination,10 rearrange-
ment,11 and addition to isatins.12 In addition, enzyme-catalyzed
asymmetric desymmetrization is known as an effective synthetic
method for producing optically active oxindoles bearing a qua-
ternary stereocenter at the 3-position,13 but nonenzymic meth-
ods have not been reported. Recently, we have developed the
chiral copper-catalyzed kinetic resolution and desymmetrization
of diols (Scheme 1).14,15 Herein, we would like to describe the
efficient synthesis of optically active 3,3-disubstituted oxindoles
using chiral copper-catalyzed asymmetric monotosylation15e of
prochiral 3,3-bis(hydroxymethyl)oxindoles.
and the enantioselectivity (entries 5 and 6).
Next, we tried the transformation of monotosylated oxindole
2d (Scheme 2). In the synthesis of 2d using 1.2 equiv of tosyl
chloride, the chemical yield and enantioselectivity were im-
proved to give the product in 81% yield and 99% ee. Monotosy-
lated oxindole 2d was benzylated with benzyl 2,2,2-
trichloroacetimidate under acidic conditions. The crude product
of 3 was used for cyanation without further purification to give
the compound 4 in 76% yield (over two steps). Chiral oxindole
derivatives bearing 3-cyanomethyl group are known as useful
synthetic intermediates.3
The absolute configuration of 2d was determined by X-ray crys-
tallographic analysis.16 Monotosylated oxindole 2d was treated
with (+)-10-camphorsulfonyl chloride, giving the sulfonate ester
5, which was recrystallized from diethyl ether to provide fine crys-
tals after purification on silica gel column chromatography
(Scheme 3). Then, the X-ray crystallographic analysis of the sulfo-
nate ester 5 proved that the newly generated stereogenic center
was (R) (Fig. 1).
2. Results and discussion
At first, the influence of N-protecting groups in 3,3-bis(hydroxy-
methyl)oxindoles 1 was examined in chiral copper-catalyzed
desymmetrization with tosyl chloride (Table 1). The reaction using
N-Boc oxindole 1a did not proceed (entry 1). However, N-acety-
loxindole 1b gave the desired product 2b with 9% yield and 63%
ee (entry 2), and N-methoxymethyloxindole 1c improved the
enantioselectivity up to 99% ee although chemical yield was still
low (entry 3). In the case of N-methyloxindole 1d, the product
2d was obtained in 75% yield and 98% ee (entry 4). Although N-
3. Conclusion
In summary, the enantioselective synthesis of oxindoles
bearing a quaternary stereocenter at the 3-position was devel-
oped using the copper-catalyzed asymmetric monotosylation
of prochiral 1,3-diols. The reaction with N-methyl oxindole 1d
led to excellent yield and enantioselectivity. The tosylated prod-
uct was readily converted to the oxindole derivatives bearing a
3-cyanomethyl group via benzylation and cyanation. The abso-
lute configuration of monotosylated oxindole 2d was deter-
mined by the X-ray crystallographic analysis of the sulfonate
ester 5.
* Corresponding author. Tel.: +81 95 819 2429; fax: +81 95 819 2476.
E-mail address: onomura@nagasaki-u.ac.jp (O. Onomura).
0957-4166/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2010.03.015

M. Kuriyama et al. / Tetrahedron: Asymmetry 21 (2010) 1370–1373
1371
H
O
O
R1
R2
OH
OH
R1
R2
O
R1
R2
*
*
OBz
OH
Cu(II)−L*
BzCl
base
N
N
Cu(II)−L*
O
H
Ph
Ph
L*: (R,R)-Ph-BOX
Scheme 1. Asymmetric benzoylation of 1,2-diols with Cu(II)–(R,R)-Ph-BOX.
4. Experimental
Table 1
Copper-catalyzed asymmetric monotosylation of 3,3-bis(hydroxymethyl)oxindolesa
4.1. General
OH OH
OTs OH
Cu(OTf)2 (10 mol %)
All melting points are not corrected. IR spectra were obtained
with Shimadzu FT-IR-8100 and expressed in cmꢀ1 1H and 13C
(R,R)-Ph-BOX (10 mol %)
+
TsCl
(1.0 equiv)
O
O
.
K2CO3 (1.5 equiv)
CH2Cl2
N
R
N
R
2
NMR spectra were taken with Varian Gemini 300 or JEOL JNM-AL
400, and chemical shift values are expressed in ppm relative to
internal TMS. Abbreviations are as follows: s, singlet; d, doublet;
t, triplet; q, quartet; m, multiplet; br, broad. High-resolution mass
spectra (HRMS) were recorded with JEOL JMS-700N spectrometer.
Specific rotations were measured with JASCO DIP-1000. All re-
agents and solvents were used as received without further purifi-
cation. The products were isolated by silica gel column
chromatography with Merck Silica Gel 60.
rt, 24 h
1
Entry
Substrate
R
Product
Yieldb (%)
eec (%)
1
2
3
4
5
6
1a
1b
1c
1d
1e
1f
Boc
Ac
2a
2b
2c
2d
2e
2f
0
9
20
75
54
19
—
63
99
98
99
37
MOM
Me
Bn
p-MeBn
a
Reaction conditions: 3,3-bis(hydroxymethyl)oxindole 1 (0.5 mmol), p-toluene-
4.2. General procedure of the copper-catalyzed asymmetric
monotosylation of 3,3-bis(hydroxymethyl)oxindoles
sulfonyl chloride (0.5 mmol), K2CO3 (0.75 mmol), Cu(OTf)2 (10 mol %), (R,R)-Ph-BOX
(10 mol %), CH2Cl2 (2 mL), rt, 24 h.
b
Isolated yield.
Determined by HPLC.
c
To a solution of Cu(OTf)2 (0.05 mmol, 18.1 mg) and (R,R)-Ph-
BOX (0.05 mmol, 16.7 mg) in CH2Cl2 (2 mL) were added 3,3-
bis(hydroxymethyl)oxindoles 1e (0.5 mmol, 89.6 mg), K2CO3
(0.75 mmol, 104 mg), and p-toluenesulfonyl chloride (0.6 mmol,
114 mg). After stirring for 24 h at room temperature, water
(10 mL) was added. The resulting mixture was extracted with
AcOEt. The combined organic layers were washed with brine, and
then dried over MgSO4. Concentration and purification through sil-
ica gel column chromatography gave the product.
4.2.1. (+)-1-Acetyl-3-hydroxymethyl-3-(p-toluenesulfonyloxy-
methyl)oxindole 2b
Yellow oil. IR (neat): 3400, 3020, 1760, 1720, 1640, 1470 cmꢀ1
.
1H NMR (300 MHz, CDCl3): d 8.23 (d, J = 8.1 Hz, 1H), 7.62 (d,
J = 8.1 Hz, 1H), 7.42–7.10 (m, 6H), 4.46–4.38 (m, 2H), 3.93–3.81
(m, 2H), 2.63 (s, 3H), 2.45 (s, 3H), 2.04 (br s, 1H). 13C NMR
(100 MHz, CDCl3): d 176.5, 170.4, 145.2, 140.5, 132.0, 129.9,
129.6, 127.9, 126.6, 125.5, 123.4, 116.8, 69.6, 64.6, 54.5, 26.6,
21.7. 63% ee (HPLC: Daicel chiralcel OG (4.6 mmu, 250 mm), n-hex-
ane/isopropanol = 10:1, 254 nm, 1.0 mL/min, 64 min and 77 min
(enriched)). ½a D19
¼ þ47:0 (c 1.0, CHCl3). MS [HR-FAB(+)]: m/z calcd
ꢁ
for C19H20O6NS [M+H]+ 390.1011, found 390.1044.
4.2.2. (+)-3-Hydroxymethyl-1-methoxymethyl-3-(p-toluene-
sulfonyloxymethyl)oxindole 2c
Colorless oil. IR (neat): 3400, 2940, 1730, 1620 cmꢀ1 1H NMR
.
(400 MHz, CDCl3): d 7.61 (d, J = 8.3 Hz, 2H), 7.38–7.29 (m, 4H),
7.10–7.02 (m, 2H), 5.15–5.05 (m, 2H), 4.46 (d, J = 9.3 Hz, 1H),
4.37 (d, J = 9.3 Hz, 1H), 3.87 (d, J = 11.7 Hz, 1H), 3.79 (d,
J = 11.7 Hz, 1H), 3.25 (s, 3H), 2.44 (s, 4H). 13C NMR (100 MHz,
CDCl3): d 176.6, 145.0, 142.2, 132.1, 129.8, 129.4, 127.9, 126.0,
124.0, 123.5, 110.1, 71.2, 69.6, 64.1, 56.1, 54.0, 21.6. 99% ee (HPLC:
Daicel chiralcel OJ-H (4.6 mmu, 250 mm), n-hexane/isopropa-
nol = 5:1, 254 nm, 1.0 mL/min, 39 min and 43 min (enriched)).
½
a 2D0
C
ꢁ
¼ þ6:8 (c 1.0, CHCl3). MS [HR-FAB(+)]: m/z calcd for
Figure 1. X-Ray crystal structure of (R)-(+)-3-((+)-10-camphorsulfonyloxymethyl)-
1-methyl-3-(p-toluenesulfonyl)oxindole 5.
19H22O6NS [M+H]+ 392.1168, found 392.1193.

1372
M. Kuriyama et al. / Tetrahedron: Asymmetry 21 (2010) 1370–1373
OH OH
OTs OH
9H), 6.98 (t, J = 7.8 Hz, 1H), 6.69 (d, J = 7.8 Hz, 1H), 4.93 (d,
Cu(OTf)2 (10 mol %)
(R,R)-Ph-BOX (10 mol %)
J = 15.6 Hz, 1H), 4.79 (d, J = 15.6 Hz, 1H), 4.52 (d, J = 9.6 Hz, 1H),
4.40 (d, J = 9.6 Hz, 1H), 3.90–3.77 (m, 2H), 2.50 (br s, 1H), 2.42 (s,
3H), 2.29 (s, 3H). 13C NMR (100 MHz, CDCl3): d 175.7, 144.9,
143.0, 135.0, 132.1, 129.8, 129.1, 128.8, 127.9, 127.6, 126.8,
126.5, 123.9, 123.0, 109.7, 69.8, 63.9, 53.5, 43.5, 21.6, 21.0. 37%
ee (HPLC: Daicel chiralcel AS (4.6 mmu, 250 mm), n-hexane/iso-
propanol = 10:1, 254 nm, 1.0 mL/min, 17 min and 26 min (en-
+
TsCl
(1.2 equiv)
O
O
K2CO3 (1.5 equiv)
CH2Cl2
N
Me
1d
N
Me
rt, 24 h
2d
81%, 99% ee
CF3SO3H
(0.5 equiv)
BnOC(NH)CCl3
(3.0 equiv)
riched)). ½a 1D9
¼ ꢀ0:8 (c 0.9, CHCl3). MS [HR-FAB(+)]: m/z calcd
ꢁ
OTs OBn
NaCN
CN OBn
for C25H26O5NS [M+H]+ 452.1532, found 452.1525.
(4.0 equiv)
O
O
N
Me
4
CH2Cl2
rt, 24 h
DMSO
75 °C, 18 h
N
Me
3
4.3. Transformation of (R)-(+)-3-hydroxymethyl-1-methyl-3-(p-
toluenesulfonyloxymethyl)oxindole 2d
76% yield
(2 steps)
4.3.1. (R)-(+)-3-Benzyloxymethyl-3-cyanomethyl-1-methy-
loxindole 4
Scheme 2. Transformation of (R)-(+)-3-hydroxymethyl-1-methyl-3-(p-toluene-
sulfonyloxymethyl)oxindole 2d.
To a solution of 2d (0.8 mmol) in CH2Cl2 (3 mL) was added
BnOC(NH)CCl3 (2.4 mmol) at 0 °C. Then, CF3SO3H (0.4 mmol) in
CH2Cl2 (1 mL) was added slowly at 0 °C, and the reaction mixture
was stirred at room temperature for 24 h. Saturated NH4Cl was
added and the resulting mixture was extracted with AcOEt. The
combined organic layers were dried over MgSO4, and filtration
and concentration gave the crude product of (R)-3-benzyloxymeth-
yl-1-methyl-3-(p-toluenesulfonyloxymethyl)oxindole 3, which
was used without further purification.
After stirring at room temperature for 10 min, the mixture of
NaCN (3.2 mmol) and crude product 3 was stirred at 75 °C for
18 h. Then, cold water and ether were added at room temperature.
The resulting mixture was extracted with ether and the aqueous
layer was treated with 20% FeSO4. The combined organic layers
were washed with cold water and brine, and dried over MgSO4.
Concentration and purification through silica gel column chroma-
O
O
S
OTs OH
OTs O
O
Et3N (2.0 equiv)
R
N
+
O
O
CH2Cl2
rt, 6 h
N
Me
O
SO2Cl
Me
5
2d
(99% ee)
86% yield
Scheme 3. Synthesis of (R)-(+)-3-((+)-10-camphorsulfonyloxymethyl)-1-methyl-3-
(p-toluenesulfonyloxymethyl)oxindole 5.
tography
methyloxindole 4 in 76% yield (two steps). Yellow oil. IR (neat):
2250, 1620, 1260 cmꢀ1 1H NMR (300 MHz, CDCl3): d 7.38–6.92
gave
(R)-(+)-3-benzyloxymethyl-3-cyanomethyl-1-
4.2.3. (R)-(+)-3-Hydroxymethyl-1-methyl-3-(p-toluenesulfony-
loxymethyl)oxindole 2d
.
White solid of mp 119–120 °C. IR (neat): 3350, 3060, 1720,
(m, 9H), 4.50 (d, J = 2.7 Hz, 2H), 3.80 (d, J = 9.0 Hz, 1H), 3.62 (d,
J = 9.0 Hz, 1H), 3.23 (s, 3H), 3.04 (d, J = 16.5 Hz, 1H), 2.76 (d,
J = 16.5 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 175.0, 143.5, 137.3,
129.4, 128.4, 128.2, 127.8, 127.5, 124.3, 123.1, 116.2, 108.6, 73.7,
1620 cmꢀ1 1H NMR (400 MHz, CDCl3): d 7.67 (d, J = 8.3 Hz, 2H),
.
7.38–7.23 (m, 4H), 7.07 (t, J = 7.8 Hz, 1H), 6.87 (d, J = 7.8 Hz, 1H),
4.48 (d, J = 9.8 Hz, 1H), 4.28 (d, J = 9.8 Hz, 1H), 3.85 (d, J = 9.2 Hz,
1H), 3.72 (d, J = 9.2 Hz, 1H), 3.19 (s, 3H), 2.54 (br s, 1H), 2.44 (s,
3H). 13C NMR (100 MHz, CDCl3): d 175.5, 145.0, 143.8, 132.2,
129.8, 129.2, 127.9, 126.5, 124.1, 123.1, 108.6, 69.6, 63.8, 53.2,
26.3, 21.6. 99% ee (HPLC: Daicel chiralcel OG (4.6 mmu, 250 mm),
n-hexane/isopropanol = 10:1, 254 nm, 1.0 mL/min, 92 min (en-
72.2, 49.8, 26.5, 22.2. ½a D22
¼ þ16:7 (c 0.36, CH2Cl2). MS [HR-
ꢁ
EI(+)]: m/z calcd for C19H18N2O2 [M]+ 306.1368, found 306.1368.
4.3.2. (R)-(+)-3-((+)-10-Camphorsulfonyloxymethyl)-1-methyl-
3-(p-toluenesulfonyloxymethyl)oxindole 5
riched) and 98 min). ½a D22
¼ þ17:2 (c 1.0, CHCl3). MS [HR-FAB(+)]:
ꢁ
m/z calcd for C18H20O5NS [M+H]+ 362.1062, found 362.1062.
To a solution of 2d (0.5 mmol) in CH2Cl2 (3 mL) were added tri-
ethylamine (1.0 mmol) and (+)-10-camphorsulfonyl chloride
(0.6 mmol) and the mixture was stirred at room temperature for
6 h. Then, saturated NaHCO3 was added, and the resulting mixture
was extracted with ethyl acetate. The combined organic layers
were dried over MgSO4, and concentration and purification
through silica gel column chromatography gave (R)-(+)-3-((+)-10-
camphorsulfonyloxymethyl)-1-methyl-3-(p-toluenesulfonyloxym-
ethyl)oxindole 5 in 86% yield. This product was recrystallized from
diethyl ether, and X-ray crystallographic analysis was conducted.
Colorless plates of mp 109–110 °C. IR (neat): 2960, 1750, 1710,
4.2.4. (+)-1-Benzyl-3-hydroxymethyl-3-(p-toluenesulfonyloxy-
methyl)oxindole 2e
White solid of mp 123–124 °C. IR (neat): 3400, 3010, 17610,
1610 cmꢀ1 1H NMR (300 MHz, CDCl3): d 7.62 (d, J = 8.4 Hz, 1H),
.
7.34–7.15 (m, 10H), 7.02 (t, J = 7.5 Hz, 1H), 6.70 (d, J = 7.5 Hz,
1H), 4.99 (d, J = 15.9 Hz, 1H), 4.83 (d, J = 15.9 Hz, 1H), 4.52 (d,
J = 9.3 Hz, 1H), 4.41 (d, J = 9.3 Hz, 1H), 3.94–3.78 (m, 2H), 2.56
(br s, 1H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3): d 175.7,
144.9, 143.0, 135.0, 132.1, 129.8, 129.1, 128.8, 127.9, 127.6,
126.9, 126.5, 123.9, 123.1, 109.6, 69.8, 64.0, 53.5, 43.7, 21.6. 99%
ee (HPLC: Daicel chiralcel OG (4.6 mmu, 250 mm), n-hexane/iso-
propanol = 10:1, 254 nm, 1.0 mL/min, 60 min and 65 min (en-
1610, 1360, 1180 cmꢀ1 1H NMR (300 MHz, CDCl3): d 7.68 (d,
.
J = 8.4 Hz, 2H), 7.37–7.31 (m, 4H), 7.09–7.04 (m, 1H), 6.87–6.84
(m, 1H), 4.57 (d, J = 9.9 Hz, 1H), 4.41 (d, J = 9.9 Hz, 1H), 4.34 (d,
J = 9.6 Hz, 1H), 4.18 (d, J = 9.6 Hz, 1H), 3.39 (d, J = 15.0 Hz, 1H),
3.21 (s, 3H), 2.84 (d, J = 15.0 Hz, 1H), 2.45 (s, 3H), 2.37–2.17 (m,
2H), 2.07 (t, J = 4.5 Hz, 1H), 2.01–1.93 (m, 1H), 1.87 (d,
J = 18.6 Hz, 1H), 1.47–1.31 (m, 2H), 1.01 (s, 3H), 0.80 (s, 3H). 13C
NMR (100 MHz, CDCl3): d 213.7, 172.5, 145.2, 143.8, 131.9, 129.9,
129.6, 127.9, 125.3, 124.8, 123.1, 108.6, 77.2, 69.4, 68.8, 57.6,
51.7, 47.9, 47.2, 42.6, 42.3, 26.8, 26.5, 24.7, 21.6, 19.54, 19.49.
riched)). ½a 2D2
¼ þ29:5 (c 1.0, CHCl3). MS [HR-FAB(+)]: m/z calcd
ꢁ
for C24H24O5NS [M+H]+ 438.1375, found 438.1375.
4.2.5. (ꢀ)-3-Hydroxymethyl-1-(p-methylbenzyl)-3-(p-toluene-
sulfonyloxymethyl)oxindole 2f
Yellow oil. IR (neat): 3360, 2920, 1700, 1620, 1470 cmꢀ1 1H
.
NMR (300 MHz, CDCl3): d 7.60 (d, J = 8.1 Hz, 1H), 7.28–7.06 (m,

M. Kuriyama et al. / Tetrahedron: Asymmetry 21 (2010) 1370–1373
1373
8. (a) Bui, T.; Syed, S.; Barbas, C. F., III J. Am. Chem. Soc. 2009, 131, 8758–8759; (b)
Kato, Y.; Furutachi, M.; Chen, Z.; Mitsunuma, H.; Matsunaga, S.; Shibasaki, M. J.
Am. Chem. Soc. 2009, 131, 9168–9169; (c) He, R.; Ding, C.; Maruoka, K. Angew.
Chem., Int. Ed. 2009, 48, 4559–4561; (d) Galzerano, P.; Bencivenni, G.; Pesciaioli,
F.; Mazzanti, A.; Giannichi, B.; Sambri, L.; Bartoli, G.; Melchiorre, P. Chem. Eur. J.
2009, 15, 7846–7849.
½
a 2D2
C
ꢁ
¼ þ24:0 (c 0.5, CHCl3). MS [HR-FAB(+)]: m/z calcd for
28H34O8NS2 [M+H]+ 576.1726, found 576.1752.
Acknowledgment
9. (a) Ishimaru, T.; Shibata, N.; Nagai, J.; Nakamura, S.; Toru, T.; Kanemasa, S. J. Am.
Chem. Soc. 2006, 128, 16488–16489; (b) Sano, D.; Nagata, K.; Itoh, T. Org. Lett.
2008, 10, 1593–1595.
10. (a) Hamashima, Y.; Suzuki, T.; Takano, H.; Shimura, Y.; Sodeoka, M. J. Am. Chem.
Soc. 2005, 127, 10164–10165; (b) Ishimaru, T.; Shibata, N.; Horikawa, T.;
Yasuda, N.; Nakamura, S.; Toru, T.; Shiro, M. Angew. Chem., Int. Ed. 2008, 47,
4157–4161.
This work was supported by the president’s discretion fund of
Nagasaki University.
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16. Crystallographic data for (R)-(+)-3-((+)-10-camphorsulfonyloxymethyl)-1-
methyl-3-(p-toluenesulfonyloxymethyl)oxindole
5 were deposited in the
Cambridge Crystallographic Data Centre as supplementary publication
number CCDC 767295. Copies of the data can be obtained, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB21EZ, UK; fax: +44(0) 1223
336033 or e-mail: deposit@ccdc.cam.ac.uk.