Construction of chiral quaternary carbon through morita-baylis-hillman reaction: An enantioselective approach to 3-substituted 3-hydroxyoxindole derivatives

Article abstract of DOI:10.1002/chem.201002240

A new enantioselective approach to obtain a tetrasubstituted chiral center at the C3 position of oxindoles via a catalytic asymmetric Morita-Baylis-Hillman reaction has been demonstrated. This reaction provides 3-substituted 3-hydroxy-2-oxindoles in good

Full text of DOI:10.1002/chem.201002240

COMMUNICATION
DOI: 10.1002/chem.201002240
Construction of Chiral Quaternary Carbon through Morita–Baylis–Hillman
Reaction: An Enantioselective Approach to 3-Substituted 3-
Hydroxyoxindole Derivatives
Xiao-Yang Guan, Yin Wei,* and Min Shi*[a]
3-Substituted 3-hydroxy-2-oxindoles are the core struc-
tures in a variety of alkaloid natural products that have re-
cently emerged as an important class of therapeutic com-
pounds with a broad spectrum of biological activities.[1]
Chiral 3-substituted 3-hydroxyindolin-2-ones are particularly
important molecules in the field of medicinal chemistry
since their biological activities have been considered to be
derived from the substituted group at C3 position as well as
the absolute configuration of the stereogenic center. There-
fore, the development of new synthetic protocols to a C3-hy-
droxy-bearing stereogenic center with control of the abso-
lute configuration is of paramount importance. Although
several synthetic approaches have been recently reported to
construct 3-aryl or alkyl 3-hydroxy-2-oxindoles based on
transition-metal-catalyzed reactions[2] or organocatalytic re-
actions,[3] there are still a lot of challenges to develop new
catalytic asymmetric reactions and new efficient synthetic
methodologies.
However, to the best of our knowledge, there has no report
on the asymmetric MBH reaction of isatin derivatives with
electron-deficient alkenes to construct chiral 3-substituted 3-
hydroxyindolin-2-ones. Moreover, besides aldehydes and ac-
tivated imines, the MBH reactions of substituted ketones
having electron-withdrawing substituents (activated ke-
tones), such as halogenated ketones, a-diketones, a-keto
esters and a-keto lactones with activated vinyl compounds,
have also been extensively studied.[7] However, as far as we
know, there has been no report about asymmetric MBH re-
action between activated ketones and activated vinyl com-
pounds either. Herein we wish to report the asymmetric
MBH reaction of isatin derivatives with acrylates to afford
the desired chiral 3-hydroxyindolin-2-ones in good yields
with high enantioselectivities, which also represents a good
example for the asymmetric MBH reaction of activated ke-
tones with activated vinyl compounds.
Isatin and a number of its derivatives, which possess a re-
active keto-carbonyl group, have been proved to be reactive
electrophilic components for the MBH reaction.[6] Accord-
ing to the previous reports, the acrylates are often less reac-
tive in MBH reaction. The DABCO-catalyzed MBH reac-
tion of methyl acrylate with isatin derivatives would cost
several days to give the adducts in moderate yields.[6] 2-
Naphthyl acrylate which has been successfully employed in
asymmetric aza-MBH reaction,[8] could accelerate the rate
of MBH reaction,[9] therefore it was chosen in our asymmet-
ric MBH reaction using isatin derivatives as the substrates.
As shown in Table 1, reaction of N-benzylisatin 1a with 2-
naphthyl acrylate 2a in CH2Cl2 in the presence of 4-(3-
ethyl-4-oxa-1-azatricyclo[4,4,0,03,8]dec-5-yl)quinolin-6-ol
(TQO), which has been proved as an efficient catalyst for
asymmetric MBH reaction,[10] could give the corresponding
adduct 3a in 97% yield with 91% ee for 40 h at room tem-
perature. Encouraged by these results, several other substi-
tuted acrylates were tested in this reaction. Phenyl acrylate
2b was also a suitable substrate, but hexafluoroisopropyl ac-
rylate 2d gave the worst result. 1-Naphthyl acrylate 2c
could give the corresponding adduct 3c with higher enantio-
During the investigations on Morita–Baylis–Hillman
(MBH) or aza-MBH reaction[4,5] which is one of the most
À
useful and interesting carbon carbon bond-forming reac-
tions to give enantiomerically enriched a-hydroxy carbonyl
compound or a-amino carbonyl compound bearing an a-al-
kylidene group, several groups have achieved to synthesize
3-substituted 3-hydroxyindolin-2-ones via MBH reaction.[6]
[a] X.-Y. Guan, Dr. Y. Wei, Prof. Dr. M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 354 Fenglin Road
Shanghai 200032 (China)
Fax : (+86)-21-64166128
E-mail: weiyin@mail.sioc.ac.cn
mshi@mail.sioc.ac.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201002240: Spectroscopic data
of all new compounds shown in Tables 1 and 2, the detailed descrip-
tions of experimental procedures, spectroscopic data, chiral HPLC
traces and X-ray data for compounds 3v.
Chem. Eur. J. 2010, 16, 13617 – 13621
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
13617

Table 1. Survey of the reaction parameters for the TQO-catalyzed asymmetric MBH reaction of isatin deriva-
tives 1 with acrylates 2.
can be produced through equili-
bration than at room tempera-
ture. The detailed investigation
will be carried out in due
course.
Having identified the optimal
reaction conditions, we next set
out to examine the scope and
limitations of this reaction
using various isatin derivatives
1 with different substituents on
the benzene rings; the results
are summarized in Table 2. As
shown in Table 2, whether elec-
tron-withdrawing or -donating
group at 5-, 6- or 7-position of
the benzene ring of N-benzyl
isatins 1 were employed, the re-
actions proceeded smoothly to
Entry[a] R1
R2
Solvent
Yield [%][b] ee [%][c] Sign of
optical
rotation
1
Bn, 1a
2-naphthyl, 2a
Ph, 2b
1-naphthyl, 2c
CH2Cl2
CH2Cl2
CH2Cl2
3a, 97
3b, 99
3c, 92
3d, 83
3e, 90
3 f, 67
3g, 84
3h, 17
3i, 88
3c, 97
3c, 92
91
87
94
61
93
92
93
46
94
83
91
66
63
93
94
93
86
63
+
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
À
2
3
4
Bn, 1a
Bn, 1a
Bn, 1a
hexafluoroisopropyl, 2d CH2Cl2
5
9-anthracenylmethyl, 1b 1-naphthyl, 2c
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
toluene
dioxane 3c, 94
DMF
DCE
6
7
8
allyl, 1c
Me, 1d
H, 1e
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
1-naphthyl, 2c
give
yields (up to 99%) along with
high enantioselectivities
3 in good to excellent
9
Tr, 1 f
10
11
12
13
14
15
16[d]
17[e]
18[f]
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
Bn, 1a
(Table 2, entries 1–7). In the
case of products 3j and 3l, re-
crystallization of them could in-
crease ee value up to 96%
(Table 2, entries 1, 3; it was dif-
ficult to recrystallize other
products since they are not
good crystalline compounds).
Unfortunately, for 4-substitued
N-benzyl isatins, no products
3c, 69
3c, 64
3c, 85
3c, 76
3c, 60
3c, 48
CHCl3
CH2Cl2
CH2Cl2
CH2Cl2
[a] All reactions were carried out with 1 (0.1 mmol) and 2 (0.2 mmol) in the presence of TQO in 1.0 mL of sol-
vent. [b] Isolated yields. [c] Determined by chiral HPLC. [d] At 08C. [e] At À208C. [f] At À408C.
selectivity along with a slight sacrifice in yield. Next, we
chose 2c as the acrylate and a series of isatin derivatives
with different N-substituents such as 9-anthracenylmethyl,
allyl, methyl and trityl (Tr) to investigate the effects of steric
hindrance. It was found that using different isatin derivatives
there were no significant effects on the enantioselectivity.
However, employing isatin without N-substituent led to the
low yield and ee. Solvent effects were subsequently exam-
ined using N-benzyl isatin 1a and 1-naphthyl acrylate 2c as
the reactants. Toluene and other chlorinated solvents such
as 1,2-dichloroethane (DCE) and chloroform were suitable
for this reaction to give 3c with high ee value. But 1,4-diox-
ane and DMF gave poor enantioselectivities. In the presence
of CH2Cl2, decreasing the temperature to 0 or À408C, both
the yields and ee value declined remarkably. The reason
why both the yields and ee value declined remarkably at
lower temperature (Table 1, entries 16–18) is probably as-
cribed to the alteration of hydrogen-bond strength between
phenolic hydroxyl group and the in situ generated enolate
intermediate at lower temperature which might introduce
detriment to the activity and enantioselectivity. Another
possibility is that the rate of the retro-aldol process from in-
termediate B becomes rather slow at lower temperature.
Namely, at lower temperature, intermediate B is difficult to
return to A and isatin derivatives, so that more R product
were obtained (Table 2, entries 8 and 9), presumably due to
the steric hindrance of the 4-substitution. We again tested
whether the more sterically congested N-substituent has an
effect on enantioselectivity. Isatin 1q was used in this reac-
tion under identical conditions, but the ee value had just
been slightly improved up to 88% (Table 2, entry 10). Ac-
cording to the results shown in Table 1, Tr was also an effec-
tive substitution, which could give ee value as high as Bn.
Several N-Tr isatin derivatives were examined in this reac-
tion. They gave the corresponding adducts with higher enan-
tioselectivities than Bn, just with a little detriment to yields.
The absolute stereochemical assignment of the adduct 3v
has been determined to be S, which was based upon a
single-crystal X-ray diffraction analysis (Figure 1).[11]
We also tried the MBH reaction of isatin derivatives with
methyl vinyl ketone (MVK), the MBH adduct I was at-
tained in 57% yield with 94% ee catalyzed by TQO in
CH2Cl2. The major byproduct is compound II which is a 1:2
adduct of 1a and MVK because of high reactivity of MVK.
However, after lots of attempts we could not improve both
of the yield and the enantioselectivity of adduct I or II
(Scheme 1)
Synthesis of 3,4-disubstituted pyrrolidin-2-one derivatives
has been investigated extensively in connection with the
design of conformationally restricted analogues of biologi-
13618
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ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 13617 – 13621

Construction of Chiral Quaternary Carbon
COMMUNICATION
Table 2. Asymmetric MBH reaction of N-protected isatin derivatives 1
with 1-naphthyl acrylate 2c catalyzed by TQO.
cally active amino acids and with the usefulness as inter-
mediates in the synthesis of biologically active nonproteino-
genic amino acids.[6c,d] Especially, the synthesis of 3-hydroxy-
pyrrolidin-2-one derivatives has received much attention.
From our enantioselective MBH adducts, we could easily
obtain chiral 3-aryl-3-hydroxypyrrolidin-2-ones. For exam-
ple, MBH adduct 3c with 93% ee could react with benzyla-
mine in methanol to give 4 in 87% yield along with 91% ee
(Scheme 2).[6c,d]
Entry[a] R1
R2
Yield [%][b] ee [%][c] Sign of
optical
rotation
1
2
3
4
5
6
7
8
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
Bn
6-Br
5-Br
5-F
3j, 99
88 (96)[d]
À
3k, 95
3 L, 99
3m, 96
88
+
89 (96)[d]
À
5-Cl
87
89
93
87
–
+
5-Me 3n, 82
7-Br 3o, 95
7-CF3 3p, 87
4-Cl
4-Br
À
À
À
–
–
n.d.[e]
n.d.[e]
+
9
–
Scheme 2. Synthesis of 3-aryl-3-hydroxypyrrolidin-2-one
4 from the
10
11
12
13
14
15
3,5-dimethylbenzyl 5-Cl
3q, 99
3r, 89
3s, 88
3t, 90
88
94
91
87
92
94
MBH adduct 3c.
Tr
Tr
Tr
Tr
Tr
5-Cl
5-F
5-Br
5-Me 3u, 70
6-Br 3v, 87
+
À
+
Our product 4 possesses the core structure of 1,3,3,4-tetra-
substituted pyrrolidines, which are the potent CCR5 antago-
nists and have been recently studied by Ma and co-work-
ers.[12] According to their work, compound 6, which dis-
played highly potent and selective inhibition of CCR5-de-
pendant HIV-1 replication, could be easily synthesized start-
+
S, +
[a] All reactions were carried out with 1 (0.1 mmol) and 2c (0.2 mmol) in
the presence of TQO in 1.0 mL of solvent. [b] Isolated yields. [c] Deter-
mined by chiral HPLC. [d] After being recrystallized once from petrole-
um ether and CH2Cl2. [e] n.d.=not determined.
ing from 3-aryl-3-hydroxypyrrolidin-2-one
5 which was
obtained through three-step synthesis from DABCO-cata-
lyzed MBH reaction of methyl acrylate with ethyl benzofor-
mate (Scheme 3).[12] Our method described above offers a
new efficient way to synthesize optically active 1,3,3,4-tetra-
substrituted pyrrolidines with an amino group induced on
the benzene ring, which could afford diversiform compounds
for the evaluation of biological activities.
Scheme 3. Synthesis of 1,3,3,4-tetrasubstituted pyrrolidine 6.
The observed enantioselectivity may be rationalized via a
reaction mechanism depicted in Scheme 4. Based on cur-
rently accepted reaction mechanism for MBH reaction,[13]
Michael addition of TQO to acrylate forms enolate A,
which in turn undergoes aldol reaction with the isatin deriv-
ative to furnish an equilibrium mixture of several diastereo-
mers. Among them, there would be two intermediates B
and C that are stabilized through hydrogen-bonding be-
tween the carbonyl group and the phenolic OH. Taking the
repulsion between the ester group and the N-substituents of
isatin into account, intermediate B suffers from severer
Figure 1. ORTEP drawing of compound 3v.
Scheme 1. MBH reaction of N-benzyl isatin 1a with MVK.
Chem. Eur. J. 2010, 16, 13617 – 13621
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
13619

M. Shi, Y. Wie and X.-Y. Guan
General procedure for TQO-catalyzed MBH reactions of isatin deriva-
tives 1 and acrylates 2: Isatin derivatives 1 (0.1 mmol), acrylates 2
(0.2 mmol), TQO (0.01 mmol) and solvent (1.0 mL) were added into a
Schlenk tube. The reaction mixture was stirred at room temperature for
40 h, then the solvent was removed under reduced pressure and the resi-
due was purified by a flash column chromatography.
Compound 3a: White solid (42 mg, 97%); m.p. 161–1638C; 1H NMR
(CDCl3, 300 MHz, TMS): d = 3.78 (s, 1H, OH), 4.86 (d, 1H, J=15.6 Hz,
NCH), 4.95 (d, 1H, J=15.6 Hz, NCH), 6.71 (d, 1H, J=7.5 Hz, Ar), 6.74
(s, 1H, =CH), 6.95 (s, 1H, =CH), 6.98 (dd, 1H, J1 =2.4, J2 =8.7 Hz, Ar),
7.07 (t, 1H, J=7.8 Hz, Ar), 7.13–7.16 (m, 3H, Ar), 7.21–7.34 (m, 5H,
Ar), 7.44–7.47 (m, 2H, Ar), 7.70–7.82 ppm (m, 3H, Ar); 13C NMR
(CDCl3, 75 MHz, TMS): d = 44.1, 76.2, 109.9, 118.5, 120.7, 123.2, 123.8,
125.7, 126.5, 127.2, 127.4, 127.58, 127.63, 128.6, 129.3, 130.2, 131.4, 133.5,
135.1, 138.8, 143.6, 147.6, 163.2, 176.4 ppm; IR (CH2Cl2): n˜ = 3352, 3058,
1728, 1701, 1613, 1510, 1488, 1467, 1356, 1315, 1265, 1208, 1157, 1042,
961, 854, 732, 697 cmÀ1; MS (ESI): m/z (%): 436.3 [M+H]+ (100);
HRMS (MALDI): m/z: calcd for C28H21NNaO4: 458.1363; found:
458.1363 [M+Na]+; [a]D20
= + 6.6 (c = 1.05, CHCl3); HPLC: OD
column;
l = 214 nm; eluent: hexane/isopropanol 80:20; flow rate:
0.7 mLminÀ1; tmajor =20.83 min, tminor =33.40 min; ee = 91%.
Acknowledgement
We thank the Shanghai Municipal Committee of Science and Technology
(08dj1400100-2), National Basic Research Program of China ACHTUNGTRENNUNG(973)-
2010CB833302, and the National Natural Science Foundation of China
for financial support (20872162, 20672127, 20821002, 20732008 and
20702059) and also thank Sun Jie for performing X-ray diffraction.
Scheme 4. Proposed mechanism.
steric hindrance than intermediate C. Thus, the difference in
the reaction rate of subsequent proton transfer and elimina-
tion step of B and C would result in (S)-enriched enantiose-
lectivity for the adduct 3v through equilibration.
Keywords: asymmetric catalysis · Morita–Baylis–Hillman
reaction · isatin · organocatalysis · oxindoles
In summary, we report for the first time a TQO-catalyzed
asymmetric MBH reaction of isatin derivatives with acryl-
ates to afford 3-substituted 3-hydroxy-2-oxindoles in good
yields with high enantioselectivities, which demonstrates an
efficient synthetic method for the catalytic asymmetric con-
struction of quaternary stereogenic center. This is also the
first asymmetric MBH reaction of activated ketones with
electron-deficient alkenes. The MBH adducts 3-substituted
3-hydroxy-2-oxindoles could be easily transformed to 3-aryl-
3-hydroxypyrrolidin-2-ones with chirality remaining, which
are the precursors of promising drug candidates for the
treatment of HIV-1 infection. Efforts are in progress to elu-
cidate further mechanistic details of these reactions and to
understand their scope and limitations. We are also synthe-
sizing optically active 1,3,3,4-tetrasubstrituted pyrrolidines
with different structures and testing their biological activi-
ties.
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18.1417(13) ꢄ, a=90, b=90.230(2), g=908, V=3263.5(4 ꢄ3; space
group: P21/n, Z=4, 1calcd =1.357 gcmÀ3
, F000 =1368, R1=0.0475,
wR2=0.0863. diffractometer: Rigaku AFC7R. CCDC-777629 con-
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Received: August 5, 2010
Published online: November 19, 2010
Chem. Eur. J. 2010, 16, 13617 – 13621
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
13621