Asymmetric Intermolecular Rauhut?Currier Reaction for the Construction of 3,3-Disubstituted Oxindoles with Quaternary Stereogenic Centers

Article abstract of DOI:10.1002/adsc.201700649

A remote cross Rauhut?Currier reaction utilizing vinyl ketones and para-quinone methides derived from isatins was realized, which was successfully catalyzed using bifunctional phosphines, furnishing chiral 3,3-disubstituted oxindoles in excellent enantioselectivities and high yields. The mechanistic studies demonstrated the key role of the alkyl hydrogen of the vinyl ketones, which conceivably interacted with the para-quinone methide carbonyl group via the hydrogen bond, offering a new insight for the design of novel asymmetric reactions. (Figure presented.).

Full text of DOI:10.1002/adsc.201700649

Title: Asymmetric Intermolecular Rauhut-Currier Reactions for the
Construction of 3,3-Disubstituted Oxindoles with Quaternary
Stereogenic Centres
Authors: Hongyu Wang, Kaiye Wang, Yunquan Man, Xiaonan Gao,
Limin Yang, Yanfei Ren, Na Li, Bo Tang, and Gang Zhao
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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using the Digital Object Identifier (DOI) given below. The VoR will be
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the VoR from the journal website shown below when it is published
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700649
Link to VoR: http://dx.doi.org/10.1002/adsc.201700649

Advanced Synthesis & Catalysis
10.1002/adsc.201700649
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Asymmetric Intermolecular Rauhut–Currier Reaction for the
Construction of 3,3-Disubstituted Oxindoles with Quaternary
Stereogenic Centers
†
,a,b
†,a
a
a
a
Hongyu Wang,
Kaiye Wang, Yunquan Man, Xiaonan Gao, Limin Yang, Yanfei
,a b
a
,a
Ren, Na Li,* Bo Tang,* and Gang Zhao
a
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized
Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of
Education, Institute of Molecular and Nano Science, Shandong Normal University, Jinan 250014, P. R. China.
[
E-mail: tangb@sdnu.edu.cn, lina@sdnu.edu.cn]
b
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
†
These authors contributed equally to this paper
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A remote cross Rauhut–Currier reaction utilizing functionalized 3,3-disubstituted oxindoles (Scheme
vinyl ketones and para-quinone methides derived from 1B).
isatins was realized, which was successfully catalyzed
using bifunctional phosphines, furnishing chiral 3,3-
disubstituted oxindoles in excellent enantioselectivities and
high yields. The mechanistic studies demonstrated the key
role of the alkyl hydrogen of the vinyl ketones, which
conceivably interacted with the para-quinone methide
carbonyl group via the hydrogen bond, offering a new
insight for the design of novel asymmetric reactions.
Keywords: Rauhut–Currier reaction; quaternary
stereocenters; remote stereogenic center; asymmetric
catalysis; organocatalysis
3
-Arylindoles with quaternary stereogenic centers
represent important structural units that exist in
pharmaceutical compounds and biologically-active
natural
products,
such
as
(+)-asperazine,
[1]
idiospermuline and SM-130686 (Scheme 1A).
Therefore, the development of efficient synthetic
methods for the construction of these molecules has
sparked many research efforts in the past decades.
Recently, a proof-of-concept study showed a
powerful approach for preparing optically active
molecules in which electrophiles were attached to 3-
aryloxindoles. Moreover, the concept has been
extended to many enantioselective variations for the
construction of these valuable molecules, including
[
2]
[3]
4]
the Mannich reactions, Michael addition reactions,
N
[
S 2 reactions and various cross-coupling reactions,
which use both organocatalysts and metal catalysts.
Although many methods for preparing 3-
aryloxindoles bearing electrophilic groups have been
discovered, searching for new strategies for
synthesizing 3-aryl oxindoles with nucleophilic
groups is an attractive goal for obtaining diversely
Scheme 1. (A) Representative bioactive molecules; (B)
3,3-disubstituted oxindoles with electrophiles and
nucleophiles; (C) intermolecular Rauhut–Currier reactions;
(
D) intermolecular remote Rauhut–Currier reactions.
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201700649
The intermolecular Rauhut–Currier reaction,
have been essential for previous preparations of 3-
[10]
known since 1963, uses two structurally diverse
olefins for the production of fine chemicals, and has
attracted considerable attention for the synthesis of
valuable compounds.[ In particular, the asymmetric
Rauhut–Currier reaction stands out as a simple but
efficient strategy for the construction of chiral carbon
centers. Furthermore, various chiral Lewis base
catalysts, including nucleophilic nitrogen, phosphine
and sulfur donor atoms, have been successfully used
for the asymmetric Rauhut–Currier reaction (Scheme
aryloxindoles.
Herein we report the first
asymmetric remote cross Rauhut–Currier reactions
between vinyl ketones with widely available para-
quinone methides derived from isatins using chiral
Lewis base catalysts to yield variations of 3 with
excellent enantioselectivities and yields.
5]
Table 1. Screening conditions for the asymmetric remote
[
a]
cross Rauhut–Currier reaction.
[6]
1
C). To the best of our knowledge, general methods
for the formation of quaternary carbon centers with
either the regular or asymmetric Rauhut–Currier
reaction have yet to be developed, despite focused
research reported in this area. This can be attributed
to the lack of efficient selectivity control and the
lower reaction activity of disubstituted alkenes.
Therefore, novel methods should be investigated to
resolve these challenging problems.
Solvent Time(h) Yield(%)[b]
e.r.[c]
Entry Cat.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
I
II
CH
CH
CH
CH
CH
CH
CH
2
2
2
2
2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2
2
2
2
2
54
18
42
54
60
48
54
48
36
60
54
48
30
41
99
98
98
37
25
17
Trace
90
Trace
95
Trace
96
58:42
89:11
96:4
95:5
67:33
89:11
63:37
-
15:85
-
5:95
-
95:5
91:9
92:8
69:31
89:11
60:40
95:5
74:26
96:4
92:8
III
IV
V
VI
VII
2
2
2
2
2
2
2
2
2
2
2
2
2
2
VIII CH
IX
X
CH
CH
CH
CH
0
1
2
3
4
5
6
7
8
9
0
1
2
XI
XII
III
III
III
III
III
III
III
III
III
III
CHCl
3
Toluene 45
EtOAc 24
CH CN 80
Acetone 18
92
98
71
96
3
Figure 1. The catalysts screened in this study.
MeOH
24
30
54
54
96
44
92
79
79
[
[
[
[
d]
e]
f]
CH
CH
CH
CH
2
2
2
2
Cl
2
Cl
2
Cl
2
Cl
2
Remote enantiocontrol has emerged as an
important field for the construction of remote chiral
centers. However, the relatively low reactivity of 1,6-
conjugate addition reactions is a major challenge for
the remote enantiocontrol of these type of
g]
47
[
a] Unless otherwise noted, all reactions were carried out
with 1a (0.05 mmol) and 2a (0.10 mmol) catalyzed by a
bifunctional chiral phosphine (5 mol%) in solvent at room
temperature. [b] The isolated yield. [c] Determined by
chiral HPLC analysis. [d] 2 equiv of H O was added. [e] 2
2
equiv of PhOH was added. [f] 20 mg 4 Å MS were added.
[g] The reaction was performed at 0 °C.
[7]
transformations. The rational design of substrates
and catalysts has helped, and at present, a variety of
interesting substrates have been developed for the
enantioselective construction of chiral products with
remote stereogenic centers.[
8]
Meanwhile, para-
quinone methide as an important synthon has been
widely applied to prepare chiral functional products,
since it was first reported by the groups of Fan and
Initially, the reaction between 1a and 2a catalyzed
Jørgensen.[9] The realization of the remote cross
by bifunctional organophosphines was carried out in
CH
2
Cl at room temperature. The reaction proceeded
2
Rauhut–Currier reaction is therefore an important
development for the construction of chiral products
smoothly using catalyst I, and 41% yield was
obtained by stirring for 54 h; however, low
enantioselectivity was achieved (Table 1, entry 1).
Informed by our previous work, in which H-bonding
interactions were demonstrated to play a vital role in
(
Scheme 1D). Considering this, the novel
paraquinone methides derived from isatins reported
in this paper were considered as promising substrates
for the construction of chiral 3,3-disubstituted
oxindoles using the challenging remote cross
Rauhut–Currier reaction. Notably, anhydrous and
anaerobic reaction conditions can be avoided, which
[11]
improving the enantioselectivities, we investigated
the influences of thiourea and urea with different
groups derived from
L
-phenylalanine. Among the
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201700649
catalysts I-V, the thiourea catalyst III bearing 3,5-
With the optimized conditions, we continued to
explore the scope of the asymmetric remote cross
Rauhut–Currier reaction (Table 2). Methyl vinyl
ketone was first examined with 1a, and the reaction
proceeded faster compared to 2a, which could be
attributed to the steric influence of the ethyl group of
2a. In particular, 3b could be scaled up to a gram-
level furnishing 1.2 g without the loss of
enantioselectivity (95.5:4.5 e.r., 96% yield in 24 h).
Investigations into the effects of different protecting
groups on the nitrogen atom of 1, including methyl,
benzyl, p-methoxybenzyl (PMB), p-nitrobenzyl
(PNB), allyl and propargyl groups, showed that the
CF groups was found to be the optimal one for this
3
reaction (98% yield, 96:4 e.r.) Further examination of
the chiral backbone with thiourea was performed to
improve the enantioselectivity of the product, but no
improvements in performance were found (Table 1,
entries 6-10). The catalyst derived from
D
-
phenylalanine was also examined, and excellent
enantioselectivity with an opposite configuration was
maintained (Table 1, entry 11). Meanwhile β-ICD
was found to be unsuitable for this reaction (Table 1,
entry 12). Other reaction parameters, including the
solvent, additives and temperature, were investigated
for the overall reaction optimization. Protic solvents
and strong polar solvents exhibited certain
detrimental effects on the enantioselectivities of the
products (Table 1, entries 13-18). The additives were
unfavorable for improving the ee values including
asymmetric
reactions
exhibited
excellent
stereoselectivities regardless of the electron-
withdrawing or electron-donating nature of the
groups. Furthermore, different substituents of 1 were
also explored in detail. Regardless of the electronic
and steric properties of the substituents on the
benzene ring, all the reactions proceeded smoothly to
afford the corresponding products with excellent
enantioselectivities, Moderate yields were obtained
with substituents on the 6 position of the benzene ring.
The absolute configuration of 3n was determined to
be R by X-ray crystallographic analysis (see SI) and
the other products were analogously determined.
To further test the potential of these asymmetric
reactions using 1, activated olefins were investigated
H O, PhOH, 4 Å MS, however, trace water
2
accelerated the reaction rate. Lowering the
temperature slowed the reaction rate, and no higher
ee values were obtained (Table 1, entry 19-22).
Table 2. Examples of vinyl ketones with para-quinone
[
a]
methides derived from isatins.
(
see SI). Remarkably, the methyl group in 1a greatly
improved the enantioselectivity and yield. However,
replacing the methyl group with hydrogen, phenyl or
phenoxy lowered the yield and enantioselectivity. To
investigate the mechanism of the reaction, an isotope
experiment was performed by adding D O (2 equiv)
2
1
into the mixture (Scheme 2A). From the H-NMR
spectrum of the corresponding product 3b, the methyl
group of 2b was 59.3% deuterated (see SI), while the
hydroxyl group of 3b remained undeuterated. Hence,
it can be assumed that the methyl group of 2b and
trace water are key factors for controlling the
stereoselectivity and increasing the yield of the
remote cross Rauhut–Currier reaction. In addition,
Yu and co-workers showed with theoretical
calculations that H O can accelerate proton transfer in
2
13]
[
[
3+2] cyclization. A non-linear effect experiment
that has been used for certain asymmetric reactions
catalyzed by organophosphines was implemented to
[11]
investigate the catalytic mechanism.
linear effect was observed using this experiment for
b catalyzed by III (see SI). According to these
A general
3
results and previous work, we tentatively proposed a
possible transition state (TS) to explain the
stereochemical results of the remote cross Rauhut–
Currier reaction (Scheme 2B). Reaction of the
organophosphine with methyl vinyl ketone forms a
zwitterion by a synergistic action of its bifunctional
groups. In addition to the interaction of the N-H bond
of the phosphine and carbonyl group of 1a, the H-
bond (C-H-O) between the methyl group of 2b and
the other carbonyl group of 1a simultaneously
reduces the space between the two compounds. The
electrophile 1a might approach the zwitterion from
[
a] Reactions were carried out under the optimized
conditions as shown in Table 2. Yields of 3 were isolated
yields. The e.r. was determined by chiral HPLC analysis.
Supplementary crystallographic data for 3n can be found
in CCDC 1538520.
MeOC
[
12]
2 6 4
PNB, p-NO C H ; PMB, p-
6
4
H .
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201700649
the Si face to minimize the steric repulsion of the
catalyst.
To illustrate the utility of the method, some
representative transformations were performed as
shown in Scheme 2C. The tert-butyl group of 3 can
enantioselectivities and yields catalyzed by III under
mild conditions. Moreover, the mechanistic study
revealed that the alkyl hydrogen of the vinyl ketone
plays an important role in improving both the yield
and the enantioselectivity. We anticipate that this
method will be valuable for new reactions and
synthetic strategies. Novel asymmetric reactions
based on the para-quinone methides derived from
isatins are currently under way in our lab.
be easily removed under mild conditions using AlCl
without the loss of enantioselectivity. Meanwhile, the
cross-coupling reaction between 5a and PhB(OH)
was carried out catalyzed by Cu(OAc) , the
corresponding product was obtained in high yield.
The transformation of 3b with p-ClC SH was
3
2
2
H
6 4
performed under basic conditions, and gave the Experimental Section
corresponding product 4 in high yield and excellent
enantioselectivity. Finally, the reaction of RMgBr
with the C=O group in 3 was attempted to prepare
tertiary alcohols, and excellent results were obtained.
General procedure for the asymmetric intermolecular
Rauhut–Currier reaction
To a solution of para-quinone methide 1 (0.05 mmol) in
2 2
CH Cl (1 mL), methyl vinyl ketone 2 (0.10 mmol) and
catalyst (5 mol%) were sequentially added. The mixture
was stirred at room temperature and monitored by TLC.
The pure products (3a-3y) were obtained via flash
chromatography (PE: EA = 4:1) as white solids.
Acknowledgements
Financial support from the 973 Program (2013CB933800),
National Natural Science Foundation of China (21390411,
2
1535004, 21422505, 21375081 and 21602125), Natural Science
Foundation for Distinguished Young Scholars of Shandong
Province (JQ201503), Natural Science Foundation of Shandong
Province (ZR2016BQ38) and a Project of Shandong Province
Higher Educational Science and Technology Program (J16LC14)
is gratefully acknowledged.
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