Self-assembled organic nanotube promoted allylation of ketones in aqueous phase

Article abstract of DOI:10.1039/c9cc00941h

A self-assembled organic nanotube was found to promote the allylation of ketones in the aqueous phase.

Full text of DOI:10.1039/c9cc00941h

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DOI: 10.1039/C9CC00941H
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Self-assembled Organic Nanotube Promoted Allylation of Ketones
in Aqueous Phase
Hui Sun,ab Jian Jiang, *b Yimeng Sun,b Qingwu Zhang,*a and Minghua Liu *bc
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A self-assembled organic nanotube was found to promote the interaction of multi-hydrogen bonds.9 Thus, it is appealing if
allylation of ketone reaction in aqueous phase.
the selective allylation of ketone could be performed in
aqueous phase and under mild conditions using
supramolecular catalytic system.
a
Multiple non-covalent interactions are involved in enzyme for
activating substrates and stabilizing reaction transition state,
thus lowering the activation energy and promoting the
reaction under mild condition.1 With the aim of mimicking
enzyme, artificial supramolecular catalysts have been
developed via non-covalent self-assembly of functional units.
The catalytic performances, such as the reactivity and
enantioselectivity, have been significantly improved in some
supramolecular catalysis systems.2 Especially, the reactivity
could be enhanced hundreds of times in self-assembled cage
catalytic system.3 Therefore, it is highly desirable to develop
self-assembled supramolecular catalytic system for promoting
the inert or unfavorable reactions under mild conditions.
Previously, we have developed self-assembled metal-
nanotube to catalyze asymmetric Diels-Alder, Mukaiyama aldol
reactions and both significantly increased reactivity and
enantioselectivity were obtained in comparison with
monomolecular component.10 Herein, the self-assembled
nanotube was employed for promoting the allylation of ketone
reaction. It was found that the tetraallyltin which acted as an
allylating reagent was able to integrate on the nanotube.
Interestingly, through such c0-assembly, ketone could be
efficiently activated by the synergistic effect from Sn species
and the hydrogen bond effect from nanotube. The reaction
progressed smoothly in the aqueous media together with
moderate enantioselectivity.
HDGA, as shown in Figure 1, was used to as a starting
building block for obtaining self-assembled nanotube. In
experiments, HDGA was firstly added into water and heated to
dissolve into a transparent solution. Then a hydrogel with was
formed upon cooling.10 During such process, self-assembled
helical nanotube was formed.10 Acetophenone was selected
as ketone substrate, and several allylating reagents were
selected as allylic precursors. Both the ketone substrate and
allylating reagents were added into aqueous dispersion of
HDGA nanotube and the reaction was carried out at room
temperature. The results were shown in Figure 1. Almost no
Allylation of carbonyl compounds offers an efficient method
to prepare allylic alcohols, which are important bioactive
5
intermediates.4, However, it is still more challenging to
synthesize the tertiary homoallylic alcohols via allylation of
ketone due to the fact that the ketone is more inert than
aldehyde toward the catalyst.6 A series of Lewis acids, such as
Ti (IV), In (III), Cu (II), Cr (III), Fe (II) and Zn (II) species have
been employed for activating ketone and promoting the
reaction.7 For these species, higher amounts of catalysts were
needed in some cases and the reactions were usually
8
performed in organic solvent system.7,
In the enzyme
catalysis system, ketone is generally activated via synergistic
reaction
happened
when
allyltriphenyltin
(1),
allyltributylstannane (2), allylboronic acid pinacol ester (3)
were used as allylating reagents. However, the reaction
progressed smoothly when tetraallyltin (4) was employed as
the allylic precursor, and 91% yield was obtained after 24 h
(Figure 1). While an extra Lewis acid was always needed for
catalyzing the reaction in previous researches,7 here, only the
self-assembled nanotube was found to promote the reaction.
a.
School of Chemical & Environmental Engineering, China University of Mining &
Technology, Beijing, PR China, 10083, P. R. China. E-mail:
zhangqingwu@tsinghua.org.cn
b. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for
Excellence in Nanoscience, Nanophotonics Research Division, National Center for
Nanoscience and Technology (NCNST) No.11 ZhongGuanCun BeiYiTiao, 100190
Beijing, P.R. China. E-mail: Liumh@iccas.ac.cn, jiangj@nanoctr.cn
c. Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Colloid,
Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese
Academy of Sciences, No.2 ZhongGuanCun BeiYiJie, 100190, Beijing P. R. China.
Electronic
Supplementary
Information
(ESI)
available:
See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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(entry 9). Finally, in consideration of heterogeneous system of
View Article Online
HDGA nanotube dispersion, HexadecDaOneI:d10io.1i0c39a/Cc9idC,C0w09h4ic1Hh
forms amorphous precipitation in water, was also used as
activator, and almost no reaction happened (entry 10). These
results indicated that self-assembled HDGA nanotube played a
vital role in promoting the reaction.
The substrate scope of the reaction was further
investigated and the results were shown in Table 2. When
para-methyl acetophenone was used as a substrate, 72% yield
of product was obtained (Table 2, entry 1). The yield was
decreased to 44% in case of electron donor para-methoxy
substituted acetophenone as the substrate (Table 2, entry 2).
Nearly full conversion were reached when para-(fluoro, nitro
and bromo) acetophenone were used as substrates, indicated
that electron-withdraw groups on the benzene were more
favorable for the reaction (Table 2, entry 3-5). Also, when
acetonaphthone was employed as a substrate, 88% yield was
reached, indicating that this catalytic system was efficient on a
range of substrates in aqueous media.
Figure 1 Allylation of ketone in aqueous dispersion of HDGA nanotube under
various Sn reagents. The reaction condition: HDGA (1 equiv), acetophenone (1
equiv), Sn reagents (1 equiv), the reaction was performed in aqueous solution at
room temperature for 24 h.
For searching the actual reason why nanotube could
promote the reaction,
a series of experiments were
performed. Firstly, considering that proton may activate the
carbonyl group of acetophenone via hydrogenation bond
interaction, a series of organic and inorganic acids were
employed instead of self-assembled nanotube. In case of
CH3COOH as activator, no product could be detected (Table 1, Table 2 substrate scope of allylation reactiona
entry 1). The reaction was retarded when CF3COOH or HCl was
O
OH
HDGA
H2O
Sn
+
involved, which gave 35% and 3% yield, respectively (entry 2
and entry 3). Furthermore, when Boc-Glu was used as organic
acid for promoting the reaction, no conversion was observed
either (entry 4). Secondly, in several polar solvents such as
DMF, DMSO and CH3OH, where HDGA completely dissolved in
a molecular state, no allylating reaction was proceeded (entry
5-7).
R
4
R
Entry
Ketone
products
Yield(%)
O
OH
1
2
72
44
O
O
OH
MeO
Table 1 Allylation of ketone under various acid mediaa
MeO
O2N
OH
O
OH
Acids
3
97
Sn
+
4
solvent
O2N
O
Entry
Acid
Solvent
H2O
Yield(%)
OH
4
5
6
96
96
88
1
2
CH3COOH
CF3COOH
HCl
-
35
3
-
F
F
H2O
O
OH
OH
3
H2O
4
Boc-Glu
HDGA
HDGA
HDGA
HDGA
H2O
Br
Br
5
DMF
DMSO
CH3OH
H2O
-
O
6
-
7
-
8b
9
89
6
-
a) In all the experiments, the reaction was carried out using tetraallyltin (1 equiv),
ketone (1 equiv), and HDGA (1 equiv) at room temperature for 24 h.
Poly(acrylic acid)
H2O
10
Hexadecanedioic acid
H2O
Tetraallyltin is prone to leave one or more allylic groups
and forms carboxylic substituted allyltin after reacting with the
organic acid.11 In HDGA nanotube system, it was difficult to
detect the actual Sn product after tetraallyltin being added
into nanotube aqueous dispersion. CD spectra were used to
investigate their interactions due to the chiral feature of
helical nanotube. The results were shown in Figure 2. No CD
signal could be detected for HDGA self-assembled nanotube in
the absorption region of tetraallyltin (Figure 2, black line).
However, a negative and positive Cotton effect at 256 nm and
a) In all the experiments, the reaction was carried out using tetraallyltin (1 equiv),
acetophenone (1 equiv), and acid (1 equiv) at room temperature for 24 h; b) the
reaction was carried out using tetraallyltin (1 equiv), acetophenone (1 equiv), and
HDGA (0.3 equiv) at room temperature for 48 h.
Thirdly, the reaction proceeded smoothly with 0.3 equiv of
HDGA nanotube in water after prolonging the reaction time
(entry 8). When Poly(acrylic acid), which possess many
carboxylic acid groups and does not form nanostructure, was
used as the activator, only trace product could be detected
2 | J. Name., 2012, 00, 1-3
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217 nm with a crossover at 238 nm was observed after (AFM, Figure S2b), the reactivity and stereoseVleiecwtAivrtiictlye Ownlianes
DOI: 10.1039/C9CC00941H
addition of tetraallyltin in HDGA nanotube dispersion (4 hours slightly decreased (Table 3, entry 3). Further increment of the
later), which was coincident with the UV-absorption of MeOH (MeOH:H2O, 1:1 and 2:1) caused the gel collapse
tetraallyltin (Figure 2, red line). This proved that tetraallyltin (Figure S2c and S2d). In these cases, both the reactivity and
was co-assembled with the nanotube during the reaction enantioselectivity decreased significantly (Table 3, entry 4 and
process and aligned in a chiral manner. Furthermore, the entry 5). Furthermore, when NaOH was involved to dissolve
morphology of assembled nanotube was investigated after the hydrogel (Figure S3), only small amount of product with
tetraallyltin being added into HDGA nanotube water poor enantioselectivity was obtained (Table 3, entry 6). These
dispersion, and nanotube structure was found to be well results indicated that the self-assembled nanotube was
preserved (AFM and TEM images were shown in Figure S1).
essential for promoting the reaction and offering the
enantioselectivity.
Based on the above research results, a hypothesis for the
reaction mechanism was proposed in Scheme 1. In the first
step, tetraallyltin was incorporated into the nanotube, as
verified from the CD spectra. When another substrate
acetophenone was added, once acetophenone was closed to
Sn site, the carbonyl group may be synergistically activated by
the Lewis acid effect of Sn complex and hydrogen bond
interaction of adjacent carboxylic acids, thus promoted the
reaction. Here, the multi-carboxylic acid groups are very
important. It should be noted that the close chiral alignment of
carboxylic acids on the self-assembled nanotube enabled the
reactivity and enantioselectivity for the allylating reaction. This
hypothesis can be supported by the following facts. When the
non-assembled organic acids were employed as activator,
tetraallyltin was also able to covalently bond to organic acid,
and acetophenone could also close to Sn precursor. However,
unlike the self-assembled nanotube where Sn sites were
surrounded by the carboxylic acid groups, the non-assembled
system has only discrete organic acid sites and could not
activate both Sn sites and acetophenone simultaneously, thus
giving low catalysis activity for the reaction. Moreover, the
curved surfaces of the nanotube could offer an asymmetric
microenvironment, which provided the prerequisite for the
enantioselectivity of reaction.
20
a
15
10
5
0
-5
225
225
250
250
275
b
1
0
275
Wavelength (nm)
Figure 2 a) CD spectra of HDGA before (black line) and after addition of
tetraallyltin (red line), upper column; b) UV/Vis spectra of HDGA before (black
line) and after addition of tetraallyltin (red line).
The enantioselectivity for the reaction was also
investigated with the acetophenone as substrate. Moderate
enantiomeric excess of the product with 25% ee was obtained
at room temperature (Table 3, entry 1). The ee value could be
o
increased to 43% when the reaction was performed at 0 C
(Table 3, entry 2).
Table 3 Allylation of ketone under mixture solution of MeOH and H2Oa
O
OH
HDGA
Sn
+
4
MeOH/H2O
Entry
Solvent (MeOH: H2O)
Yield (%)
ee (%)
25
43
15
10
4
1
2b
3
0:1
0:1
1:2
1:1
2:1
0:1
91
74
60
22
14
13
4
5
6c
3
a) In all the experiments, the reaction was carried out using tetraallyltin (1 equiv),
acetophenone (1 equiv), and HDGA (1 equiv) at room temperature for 24 h. b)
The reaction was performed at 0 oC. c) 3 equiv of NaOH was added to dissolve the
HDGA hydrogel.
The enantioselective catalytic performance of HDGA
assembly was further investigated in the methanol-H2O mixed
solvents. When the volume ratio of MeOH:H2O was 0.5:1,
where a gel was formed and nanotube structure still remained
Scheme 1 Proposed mechanism for HDGA promoting the allylation of ketone.
The first step, tetraallytin was incorporated onto nanotube via leaving one or
more allylic groups. Second, acetophenone was added, once it close to Sn sites,
it can be activated by the synergistic effect of Sn specious and carboxylic acids,
thus promoted the reaction.
This journal is © The Royal Society of Chemistry 20xx
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K. N. Clary, R. G. Bergman, K. N. Raymond and F. D. Toste,
View Article Online
Nat. Chem., 2013, 5, 100-103.
In conclusion, a self-assembled helical nanotube was found
to serve as a platform for promoting allylation of ketone in
aqueous media. When tetraallyltin was connected to the
nanotube, a catalytic transformation site was formed. Another
substrate acetophenone can be synergistically activated by the
Sn species and hydrogen bond interaction from adjacent
carboxylic acids on the nanotube, thus promoted the reaction.
While extra Lewis acid should be involved in the previously
reported molecular catalytic system for the allylation of ketone,
here, only the nanotube can work well. It demonstrated that
self-assembled architecture can provide synergistic activation
effect on both catalyst and substrate to promote the reaction.
The authors thank the National Natural Science Foundation
of China (21861132002 , 21773043, 21890734) for supporting.
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Conflicts of interest
There are no conflicts to declare.
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