Bi(OAc)3/chiral phosphoric acid catalyzed enantioselective allylation of isatins

Article abstract of DOI:10.1039/c9cc07944k

Herein, we disclosed an efficient protocol for the construction of chiral 3-allyl-3-hydroxyoxindoles via the enantioselective allylation reaction of isatins and allylboronates catalyzed by a simple binary acid Bi(OAc)₃/CPA system under mild conditions. The synthetic utility of this strategy has been demonstrated through the formal synthesis of ent-CPC-1.

Full text of DOI:10.1039/c9cc07944k

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Conformational control of nonplanar free base porphyrins:
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DOI: 10.1039/C9CC07944K
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Bi(OAc) /Chiral Phosphoric Acid Catalyzed Enantioselective
3
Allylation of Isatins†
Received 00th January 20xx,
Accepted 00th January 20xx
Jie Wang,‡Qingxia Zhang,‡Yao Li, Xiangshuai Liu, Xin Li* and Jin-Pei Cheng
DOI: 10.1039/x0xx00000x
A. Chiral oxindole type bioactive molecules:
Other bioactive indole derivatives:
HO
HO
Herein, we disclosed an efficient protocol for the construction of
chiral 3-allyl-3-hydroxyoxindoles via enantioselective allylation
reaction of isatins and allylboronates catalyzed by simple binary
Br
HO
H
HO
N
NMe
O
O
R
O
N
N
H
N
O
Br
Me
Br
N
H
H
Me
3
acid Bi(OAc) /CPA system under mild conditions. The synthetic
n-Bu
R = CH2Cl: Convolutamydine B
R = CH2OH: Convolutamydine E
O
Donaxaridine
(-)-Flustraminol B
Madindoline A
utility of this strategy has been demonstrated through the formal
synthesis of ent-CPC-1.
B. Synthetic strategies:
HO
R3
O
R1
O
General
intermediate
Optically pure 3-hydroxy-3-substituted 2-oxindole is
a
N
R1
O
R2
N
R
(
±)
privileged structural motif widely present in natural products,
drugs and bioactive compounds (Scheme 1A). And the
2
HO
Kinetic resolution
Wittig [2,3]-
rearrangement
1
R1
O
N
R
R4
substituent on the C3 position often influences the biological
activities immensely. The asymmetric synthesis of these
molecules is further pursued by the increasing demand for
modern drug research. However, most published synthetic
routes were designed aiming to single certain target
2
O
R1
O
N
R1
O
R2
B
N
R2
R4 = Allyl, OH, OBoc
rarely
Asymmetric hydroxylation
Asymmetric allylic alkylation
Carbonyl-ene reaction
Vinylogous adol
Nucleophilic allylation
C. This work: CPA and Bi(OAc)3
O
2
compound. Through the retrosynthetic analysis, chiral 3-allyl-
O
O
OH
O
P
Bi(OAc)3
HO
3
-hydroxyoxindole was considered as a general synthetic
O
+
B(pin)
O
N
N
intermediate for many bioactive chiral 3-hydroxy oxindole and
indoline derivatives (Scheme 1A). Consequently, considerable
attentions have been payed to the asymmetric synthesis of 3-
allyl-3-hydroxyoxindole type compounds in the past decade
PG
PG
Scheme 1 Representative 3-hydroxy-2-oxindole derivatives and the synthesis strategies
for 3-allyl-3-hydroxyoxindoles.
group compatibility, stability, low toxicity and overall
operational simplicity, allylboronates stand out as a uniquely
versatile allylation reagents in the research of asymmetric
(Scheme 1B). Traditional approaches to chiral 3-allyl-3-
hydroxyoxindoles include kinetic resolutions of racemic 3-allyl-
3
3
2
-hydroxyoxindoles, Witting [2,3]-rearrangement of 3-allyloxy-
1
0a,10c,11
4
5
allylation reactions.
As a result, metal complexes
-oxindoles, asymmetric hydroxylations of 3-allyloxindoles,
allylic alkylations of 3-hydroxyoxindoles, carbonyl-ene and
vinylogous aldol reactions of isatins. In recent years, the direct
6
7
mediated asymmetric allylations of ketones with allylboronates
through transmetalation pathway have been successfully
8
1
2
demonstrated. In addition, chiral binaphthols were also well
allylation of isatins, in which allylstannanes and allyl silanes
were used as nucleophilic allylation reagents, has emerged as
1
3
performed in the asymmetric allylations of ketones.
Impressively, Hoveyda has developed the easily modifiable
aminophenol-valine organocatalysts to graciously realize the
asymmetric allylations of various ketone compounds.
However, among the mentioned work, only one case of
asymmetric allylation of isatins with allylboronates has been
reported, and the number of substrates is very limited.
Recently, environmentally friendly BiX has been successfully
used for asymmetric allylations of aldehydes and imines.
Herein, we report the enantioselective allylation of isatins
catalyzed by Bi(OAc) /CPA, which delivered a number of 3-allyl-
9
an efficient and straightforward method. However, these
methods suffered from high toxicity of allylation reagents and
catalysts.
Due to the advantages of wide availability, good functional-
1
4
1
4a
3
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai
University, Tianjin 300071(P. R. China).
E-mail: xin_li@nankai.edu.cn
1
5
†
1
‡
Electronic Supplementary Information (ESI) available. See DOI:
0.1039/x0xx00000x
These authors contributed equally.
3
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COMMUNICATION
Journal Name
3
-hydroxyoxindoles in high to excellent enantioselectivities equipped with the isatins, the allylation products 3b and 3c
View Article Online
DOI: 10.1039/C9CC07944K
(Scheme 1C).
were obtained with poor enantioselectivities (Table 2).
We initiated our research by conducting the reaction of N- Although phenyl or triphenyl methyl type PGs had the aromatic
benzyl isatin 1a and allylboronic acid pinacol ester 2a in Et
room temperature in the presence of 2 mol% Bi(OAc) /2 mol% probably due to their inflexibilities (Table 2).
chiral phosphoric acid (S)-4a. As a result, the target compound phenomenon demonstrated that a flexible aromatic protecting
a was obtained with 92% yield and 36% ee (Table 1, entry 1). group may be necessary to the enantioselectivity. Based on this
2
O at rings, corresponding substrates did not perform well either,
1
6
3
This
3
Examination of several BINOL-derived chiral phosphoric acids recognition, we next investigated the different substituted
demonstrated that the substituents at the 3,3’-position of CPA benzyl PGs. As shown in Table 2, the electronic effect of benzyl,
have remarkable impacts on the outcome of the which is concerned with the π electron density, could
enantioselectivity (Table 1, entries 1-5), in which (S)-4e gave the significantly influence the stereoselectivity of the reaction,
3
best 44% ee (Table 1, entry 5). We then investigated some exhibited that the electron-withdrawing substituent (4-CF )
SPINOL-based chiral phosphoric acids with fused aromatic ring would decrease the enantioselectivity (3f), while the electron-
substituents (Table 1, entries 6-7). To our delight, promising donating substituents (4-MeO or 2,4,6-3Me) would increase the
enantioselectivity was achieved with catalyst (S)-4g (Table 1, enantioselectivities (3h and 3i). Fortunately, when fused rings,
entry 7). After that, we moved on to investigate the effects of whose are believed to form better π-π interactions, were used
solvents and found that cyclohexane was the optimal one (Table as PGs, the enantioselectivities of the products were improved
1
, entries 8-13), afforded 3a in 97% yield with 84% ee (Table 1, to a satisfactory level. In particular, the best ee value was
entry 13). Further lowing the reaction temperature or adding afforded by using 1-naphthalene methyl substituent as the
molecular sieves as additives could not improve reaction protecting group (Table 2, 3ka, 94% ee). These results clearly
outcomes (Table 1, entries 14 and 15).
showed that the π-π intermolecular interaction was
indispensable and played a critical role in the stereo-control
process, which was in agreement with our design.
a
Table 1 Optimization of the reaction conditions.
O
HO
Bi(OAc)3 (2 mol%)
Table 2 The effect of N-protecting group.a
O
B
CPA (2 mol%)
O
+
O
N
Sol. (0.2M), rt
N
O
Bn
Bn
3a
Non- or  disadvantageous PGs: poor enantioselectivities
1a
2
HO
HO
HO
HO
Ar
Ar
(
S)-4a: Ar = 9-anthryl
O
O
O
O
i
O
O
O
N
N
(
S)-4b: Ar = 2,4,6- Pr3C6H2
(S)-4f: Ar = 1-naphthyl
OH (S)-4g: Ar = 9-anthyl
N
N
O
O
O
P
P
(S)-4c: Ar = 3,5-(CF ) C H
OH
3
2
6
3
H
O
(
(
S)-4d: Ar = 4-PhC6H4
S)-4e: Ar = 1-naphthyl
H
H
H3C
Ar
Ar
3
b: 18h, 97% yield
3c: 90h, 83% yield
23% ee
3d: 28h, 94% yield
44% ee
3e: 47h, 79% yield
29% ee
Entry
CPA
4a
4b
4c
4d
4e
4f
4g
4g
4g
4g
4g
4g
4g
4g
4g
Sol.
t/h
0.5
0.5
0.5
0.5
1
1.5
0.5
2
1
1.5
5
0.5
3
49
2
Yield(%)b
92
ee(%)c
36
20
-6
24
44
36
74
45
45
55
4
40% ee
1
2
3
4
5
6
7
8
9
Et
Et
Et
Et
Et
Et
Et
2
O
2
O
2
O
2
O
2
O
2
O
2
O
Substituted benzyl PGs: good enantioselectivities and observed electronic effect
HO
HO HO HO
95
95
93
95
98
98
96
95
98
95
98
97
97
95
O
O
O
O
N
N
N
N
Me
Me
F3C
f: 4h, 98% yield
5% ee
tBu
MeO
Me
3
3g: 7h, 97% yield
78% ee
3h: 7h, 90% yield
80% ee
3i: 11h, 90% yield
85% ee
4
EA
Fused aromatic ring PGs: excellent enantioselectivities
CH
2
Cl
2
HO
HO
HO
1
1
1
1
0
1
2
3
CHCl
THF
Toluene
Cyclohexane
Cyclohexane
Cyclohexane
3
O
O
N
O
N
N
66
80
-5
d
1
4
5
3j: 10h, 85% yield, 87% ee
3k: 11h, 86% yield, 90% ee
(12h, 93% yield, 94% ee)b
3la: 24h, 53% yield, 87% ee
e
1
79
a
The reactions were carried out with 1a (0.1 mmol), 2a (0.12 mmol),
Bi(OAc) (2 mol%), and CPA (2 mol%) in 0.5 mL solvent at room
temperature. Yield of isolated products. Determined by HPLC
a
The reactions were carried out with 1 (0.1 mmol), 2a (0.12 mmol),
3
3
Bi(OAc) (2 mol%), and (S)-4g (2 mol%) in 0.5 mL cyclohexane at
b
c
room temperature. Isolated yields. The ee values were determined
d
o
e
analysis. The reaction was conducted at -10 C. 5Å molecular
sieves (40 mg) were added.
b
by HPLC analysis. The reaction concentration was 0.05 M, and the
absolute configuration of the product was identified by comparison
to the data in ref. 9c.
Previous catalyst screening results indicated that phosphoric
acids containing
π
system substituents gave better
With the optimal conditions in hand, we investigated the
enantioselectivities (Table 1). We surmised that enhancement substrate scope of this reaction (Table 3). Although most of the
of the possible weak π-π intermolecular interaction between 4-substituted isatins participated in asymmetric catalytic
substituent of CPA and protecting group of isatin might be an reactions with unsatisfactory results, in this strategy, the 4-
arguably ideal modified strategy to strengthen the chloro and 4-bromo substituted isatins could give
stereoselectivity control of our allylation reaction. In fact, when corresponding products 3kb and 3kc with excellent
the non-interaction PGs, such as methyl and acetyl, were enantioselectivities (92% and 91% ee). Furthermore, a range of
2
| J. Name., 2012, 00, 1-3
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3
-allyl-3-hydroxyoxindoles bearing either electron-donating or Table 4 Scope of allylboron reagents and α-ketoester.a
View Article Online
DOI: 10.1039/C9CC07944K
halogen atoms on C5 position of the pheny ring could be
obtained in high yields (84-96%) with good enantioselectivities
HO
HO
Me
O
B(pin)
O
N
(86-92% ee). To our delight, substrate with strong electron-
N
R'
R'
BF3K
Cl
O
Cl
withdrawing substituent NO on C5 position also tolerated this
2
3kp, 85h, 17% yield
3m, 85h, 80% yield,
1:1 dr, 90%/75% ee
54% ee
O
allylation protocol, delivered the product 3ki in a slightly
reduced enantioselectivity. In addition, this catalytic strategy
was applicable to the C6 or C7 substituted isatins, which
achieved the target products 3kj-3ks with good reactivities (80-
N
R'
Me
HO
Cl
Me Me
HO
B(pin)
R' = 1-methylene
-Naphthyl
B(pin)
O
N
R'
Cl
O
N
R'
3n, 4h, 94% yield
5% ee
Cl
9
9% yields) and good to excellent enantioselectivities (78-95.5%
3o, 30h, 77% yield
73% ee
7
ee). It is worth mentioning that the C6 or C7 substituted
a
The reactions were carried out with 1 (0.1 mmol), 2 (0.12 mmol),
substrates have not been reported in the previously asymmetric Bi(OAc) (2 mol%), and (S)-4g (2 mol%) in 2.0 mL cyclohexane at
3
1
5a
room temperature. Isolated yields. The ee values were determined
by HPLC analysis.
allylations with allylboron reagents. Finally, the disubstituted
isatins could deliver 3-allyl-3-hydroxyoxindoles 3kt and 3ku in
high yields (80% and 99%) with excellent enantioselectivities
To probe the efficiency of current asymmetric allylation
strategy in preparative synthesis, a gram-scale synthesis was
performed under optimal reaction conditions. To our delight,
the corresponding product 3ka was obtained without any loss
of reactivity and enantioselectivity (Scheme 2a). To illustrate
the synthesis applicability of this protocol, some
transformations of the allylation products were conducted.
(94.5% and 92% ee).
a
Table 3 Scope of isatins.
O
HO
Bi(OAc)3 (2 mol%)
O
B
(S)-4g (2 mol%)
R
O
+
R
O
N
R'
Cyclohexane (0.05M), rt
N
R'
O
1
2a
3
R' = 1-methylene-Naphthyl
a.
O
HO
Cl
Br
HO
F
HO
Bi(OAc)3 (2 mol%)
(S)-4g (2 mol%)
HO
HO
Cl
O
B(pin)
O
+
O
N
O
N
N
O
O
Cyclohexane(0.05M), rt
N
N
N
1-naphthyl
1-naphthyl
R'
R'
R'
kb, 95h, 90% yield
2% ee
R'
1k: 1.00 g
3.5 mmol
2a: 0.60 g
4.2 mmol
3ka: 1.02 g
3.08 mmol
3
3kc, 71h, 99% yield
3kd, 11h, 96% yield
90% ee
3ke, 3h, 94% yield
87.5% ee
9
91% ee
88% yield, 94% ee
HO
HO
HO
HO
b.
c.
d.
HO
MeO
MeO
O2N
MeO
Br
Me
CH3I
NaH, DMF, rt
NBS, AIBN
PhCl, reflux,12h
O
O
O
N
O
O
O
O
N
N
N
N
N
N
R'
R'
R'
R'
1-naphthyl
1-naphthyl
H
3
kf, 7.5h, 86% yield
3kg, 3.5h, 84% yield
87% ee
3kh, 43h, 93% yield
86% ee
3ki, 72h, 91.5% yield
78% ee
3ka,94% ee
5, 98% yield, 95% ee
6, 64% yield, 93% ee
92% ee
ref.17
HO
HO
HO
HO
HO
HO
Ph
O
O
O
O
O
2
PhN BF4
MeO
NMe
N
R'
Me
N
F
N
Cl
N
Br
O
Pd2(dba)3
DMA, rt
R'
kj, 7h, 93% yield
5% ee
R'
R'
N
N
3kl, 3h, 93% yield
89.5% ee
3km, 2.5h, 99% yield
89.5% ee
N H
3
3kk, 7.5h, 96% yield
87% ee
1-naphthyl
1-naphthyl
Me
ent-CPC-1
8
3ka, 94% ee
7, 60% yield, 94% ee
HO
HO
HO
HO
O
O
O
O
O
N
R'
O
N
R'
O
N
R'
HO
MeO
N
R'
Acrylyl chloride
NaH, rt
O
F
Cl
Br
O
Grubbs' (II)
N
o
O
N
O
3
kn, 99h, 80% yield
3ko, 3h, 92% yield
90.5% ee
3kp, 3.5h, 97% yield
92% ee
3kq, 8h, 88% yield
81% ee
THF, 0 C- rt
toluene, reflux
N
89.5% ee
Cl
1-naphthyl
Cl
1-naphthyl
Cl
1-naphthyl
Cl
HO
HO
Cl HO
HO
3kp, 93% ee
8, 94% yield, 92% ee
9, 50% yield, 93.5% ee
O
O
N
CF3 R'
O
N
R'
O
N
R'
Cl
PhCHO,
N
R'
BF •OEt2
Cl
3
DCM, 0oC - rt
Me
F
3
kr, 42.5h, 82% yield
3ks, 2h, 99% yield
78% ee
3kt, 96h, 80% yield
94.5% ee
3ku, 20.5h, 99% yield
92% ee
O
O
O
95.5% ee
O
O
N
O
a
The reactions were carried out with 1 (0.1 mmol), 2a (0.12 mmol),
O
N
O
N
Bi(OAc)
3
(2 mol%), and (S)-4g (2 mol%) in 2.0 mL cyclohexane at
N
H
Cl
1-naphthyl
room temperature. Isolated yields. The ee values were determined
10, 50% yield, 85% ee
CB2 agonist
cytotoxic activity
by HPLC analysis.
Scheme 2 Gram-scale reaction and transformations of the products.
Then, our attention was focused on the other allylboron reagents
Firstly, the allylation product 3ka could be easily converted into
compound 5 through methylation of the hydroxyl group. And
(Table 4). When potassium allyltrifluoroborate was used, the
corresponding product 3kp was obtained in 17% yield with 54% ee.
This result indicated that the substituent on the central boron atom then, by refluxing with NBS and AIBN in chlorobenzene, the
had a significant effect on the reactivity and stereoselectivity. deprotection product 6, whose enantiomer could be converted
Although α-methyl branch allylboronic acid pinacol ester showed
to pyrrolidinoindoline-type alkaloid ent-CPC-1 by means of the
poor diastereoselectivity (1:1 dr), the corresponding α-addition
1
7
reference methods,
was obtained with invariant
product 3m was obtained in good enantioselectivities (90%/75% ee).
In addition, the β-methyl branch allylboronic acid pinacol ester
enantioselectivity (Scheme 2b). In addition, compound 7
0
proceed smoothly under the optimal conditions, and gave the containing (E)-styrenyl core was afforded by a simple Pd -
desired product 3n with moderate enantioselectivity (75% ee). catalyzed Heck reaction, in which the enantioselectivity was
Moreover, 3,3-dimethylallylboronic acid pinacol ester was also
successfully used to deliver the γ-addition product 3o in 73% ee.
maintained (Scheme 2c). Moreover, the acryloylation product 8
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COMMUNICATION
Journal Name
Tan, K. W. Huang and Z. Jiang, Angew. Chem. IVnietw. EArdti.c,le2O0n1lin3e,
2, 6666-6670; (c) X. Bai, G. Zeng, T. Shao and Z. Jiang, Angew.
Chem. Int. Ed., 2017, 56, 3684-3688; (d) V. Laina-Martín, J.
Humbrías-Martín, J. A. Fernández-Salas and J. Alemán, Chem.
Commun., 2018, 54, 2781-2784.
For allylstannanes as nucleophiles, see: (a) N. V. Hanhan, A. H.
Sahin, T. W. Chang, J. C. Fettinger and A. K. Franz, Angew.
Chem. Int. Ed., 2010, 49, 744-747; (b) Y. Murata, M. Takahashi,
F. Yagishita, M. Sakamoto, T. Sengoku and H. Yoda, Org. Lett.,
could be obtained by treating 3kp with NaH and acrylyl chloride.
Following olefin metathesis cyclization catalyzed by Grubbs
second catalyst provided compound 9, which has a valuable
chiral spirocyclic oxindole skeleton (Scheme 2d). Finally, 3kp
could also be converted into fluorinated spirooxindole pyrans
5
DOI: 10.1039/C9CC07944K
9
1
0 through a spiro-Prins fluorination reaction with PhCHO
catalyzed by BF ·OEt (Scheme 2d).
3
2
In summary, we have developed a highly efficient and
enantioselective asymmetric allylation of isatins with
2
013, 15, 6182-6185; (c) T. Wang, X.-Q. Hao, J.-J. Huang, K.
Wang, J.-F. Gong and M.-P. Song, Organometallics, 2014, 33,
194-205; (d) M. Takahashi, Y. Murata, F. Yagishita, M.
Sakamoto, T. Sengoku and H. Yoda, Chem. -Eur. J., 2014, 20,
allylboronates catalyzed by a binary acid Bi(OAc)
3
/CPA system
under mild conditions. series of chiral 3-allyl-3-
A
1
1091-11100; (e) D. Ghosh, N. Gupta, S. H. R. Abdi, S. Nandi,
N. H. Khan, R. I. Kureshy and H. C. Bajaj, Eur. J. Org. Chem.,
015, 2801-2806; For allyl silanes as nucleophiles, see: (g) Z.-
hydroxyoxindoles were obtained in excellent yields with good
enantioselectivities. Low catalyst loading was also
demonstrated. The synthetic utility of this allylation strategy
has been demonstrated through the formal synthesis of ent-
CPC-1 and some valuable transformations of the allylation
products.
2
Y. Cao, Y. Zhang, C.-B. Ji and J. A. Zhou, Org. Lett., 2011, 13,
6398-6401; (h) N. V. Hanhan, Y. C. Tang, N. T. Tran and A. K.
Franz, Org. Lett., 2012, 14, 2218-2221; (i) Z.-Y. Cao, J.-S. Jiang
and J. Zhou, Org. Biomol. Chem., 2016, 14, 5500-5504.
0 For selected reviews describing stereoselective allyl addition
to carbonyl compounds, see: (a) J. W. J. Kennedy and D. G.
Hall, Angew. Chem. Int. Ed., 2003, 42, 4732-4739; (b) M. Yus,
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We are grateful to the NNSFC (Grant Nos. 21971120 and
2
1933008) for financial support.
7
774-7854; (c) H.-X. Huo, J. R. Duvall, M.-Y. Huang and R.
Conflicts of interest
There are no conflicts to declare.
Hong, Org. Chem. Front., 2014, 1, 303-320.
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1 For a review describing application of allylboron reagents,
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