"Bottom-up" embedding of the Jorgensen-Hayashi catalyst into a chiral porous polymer for highly efficient heterogeneous asymmetric organocatalysis

Article abstract of DOI:10.1002/chem.201200753

The only way is up! "Bottom-up" construction of a robust chiral porous polymer (JH-CPP) embedded with the Jorgensen-Hayashi catalyst (JH) has been successfully achieved for highly efficient heterogeneous organocatalysis. The high BET surface area, wide op

Full text of DOI:10.1002/chem.201200753

COMMUNICATION
DOI: 10.1002/chem.201200753
“Bottom-Up” Embedding of the Jørgensen–Hayashi Catalyst into a Chiral
Porous Polymer for Highly Efficient Heterogeneous Asymmetric
Organocatalysis
Chang An Wang, Zhi Kun Zhang, Tao Yue, Ya Lei Sun, Lei Wang, Wei David Wang,
Yuan Zhang, Chong Liu, and Wei Wang*[a]
Recent years have witnessed the rapid growth of enantio-
selective organocatalysis as a new tool for the asymmetric
synthesis of chiral compounds.[1] Diarylprolinol silyl ethers,
the so-called Jørgensen[2]–Hayashi[3] catalysts (Scheme 1),
represent one class of the most important organocatalysts
that activate aldehydes by an enamine mechanism[4] and
a,b-unsaturated carbonyl substrates by an iminium ion
mechanism.[5] Moreover, the Jørgensen–Hayashi catalysts
have been well-utilized in tandem and multicomponent re-
actions for the ingenious construction of complicated chiral
molecules.[6] However, high loading of organocatalysts, to-
gether with laborious separation processes has generally re-
stricted their practical applications on a large scale. Immobi-
lization of organocatalysts in a “post-synthesis” approach
may, therefore, offer a solution to these vital problems by
facilitating product separation and catalyst reuse.[7] For ex-
ample, Jørgensen–Hayashi catalysts immobilized on poly-
meric,[8] dendritic,[9] perfluoroalkyl,[10] ionic,[11] or superpara-
magnetic supports[12] have accordingly been developed. Such
“anchored” organocatalysts often suffer from tedious syn-
thetic routes, less and inhomogeneously distributed active
sites, poor stability, as well as low efficiency in mass trans-
port.[7d] In this context, the all-in-one construction of hetero-
geneous organocatalysts directly from the self-condensation
of functional building blocks through a “bottom-up” strat-
egy,[13] may possibly overcome these drawbacks. Indeed, sev-
eral pioneering applications in asymmetric organocatalysis
with bottom-up-constructed non-porous heterogeneous or-
ganocatalysts have appeared recently.[14]
(metal–organic frameworks[16,17] periodic mesoporous orga-
nosilicas,[18] porous organic polymers[19,20] and covalent or-
ganic frameworks[21]) as heterogeneous catalysts has recently
found success. Nevertheless, the bottom-up construction of
robust heterogeneous organocatalysts with both porosity
and asymmetric catalytic activity still remains a challenging
task. In 2010, we envisioned the possibility[20c] of bottom-up
construction of chiral porous organic networks with embed-
ded asymmetric organocatalysts. The idea stemmed from
the recently discovered porous organic polymers (POPs)
which can be built in one step from well-designed rigid
monomers through covalent bonds.[22,23] Very recently,
Bleschke et al.,[24] made an important contribution to this
area by introducing chiral 1,1’-bi-2-naphthol (BINOL) deriv-
atives into a microporous polymeric network, though the re-
sults of porosity (Brunauer–Emmett–Teller (BET) surface
area of 88 m2 gÀ1) and the enantioselectivity (47–56% enan-
tiomeric excess (ee)) are not satisfactory.
Herein, we report for the first time the bottom-up con-
struction of a robust chiral porous polymer (JH-CPP,
Scheme 1) embedded with the Jørgensen–Hayashi catalyst
(JH) for highly efficient heterogeneous organocatalysis. The
JH-CPP polymer was facilely synthesized by the Co2(CO)8-
mediated trimerization[20f,25] of tetrahedrally structured
building blocks (Scheme 1). With the high BET surface area
of 881 m2 gÀ1, the synthesized JH-CPP polymer contains
both micropores and, more importantly, mesopores. The per-
manent porosity of JH-CPP originates from the rigidity of
both functional and structural building blocks. Moreover, by
eliminating efficiently the “dead space” during the polymer
synthesis,[26] the rigid tetrahedral structure of the building
blocks renders the JH-CPP polymer with wide openings
and interconnected nanopores. Specifically, the constructed
mesopores greatly facilitate the mass transport process. As a
result, JH-CPP shows excellent catalytic activity in catalyz-
ing the asymmetric Michael addition of aldehydes to nitroal-
kenes.
On the other hand, solid catalysts with persistent porosity
possess the unique advantage of a large surface area, which
could greatly increase the accessibility of catalytic sites and
facilitate the mass transport process.[15] In this regard, the
bottom-up strategy for constructing porous materials
[a] C. A. Wang, Z. K. Zhang, T. Yue, Y. L. Sun, L. Wang, W. D. Wang,
Dr. Y. Zhang, C. Liu, Prof. Dr. W. Wang
State Key Laboratory of Applied Organic Chemistry
College of Chemistry and Chemical Engineering
Lanzhou University, Lanzhou, Gansu 730000 (P.R. China)
Fax : (+86)931-891-5557
We first synthesized the ethynyl-modified Jørgensen–Hay-
ashi catalyst JH as the functional building block by simple
transformation from the commercially available and cheap
starting material, (l)-proline (see Section B in the Support-
ing Information). As shown in Scheme 1, we then construct-
ed the chiral porous polymer JH-CPP from JH as the func-
E-mail: wang_wei@lzu.edu.cn
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201200753.
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with H2 hysteresis loops, which
is indicative of mesoporous
character.[27] The measured
BET surface area of JH-CPP is
881 m2 gÀ1 and the pore volume
is 0.50 cm3 gÀ1 as calculated
from the amount of N2 gas ad-
sorbed at p/p0 =0.99. From t-
plot analysis, the JH-CPP poly-
mer displays both a micropo-
rous contribution of 438 m2 gÀ1
(49.7%) and a mesoporous con-
tribution of 443 m2 gÀ1 (50.3%).
As calculated by non-local den-
sity
functional
theory
(NLDFT), the pore size distri-
bution (PSD) of JH-CPP was
found to be centered at approx-
imately 0.6 and 1.3 nm, respec-
tively (Figure 1b). The broad
PSD curves also suggest the co-
existence of micro- and meso-
pores in JH-CPP.
The chemical composition of
JH-CPP was characterized by
solid-state 13C cross-polarization
magic-angle
spinning
(CP/
MAS) NMR
spectroscopy
(Figure 2). The 13C CP/MAS
NMR signals at d=À4, 19, 26,
47, 65, 83, 130, and 146 ppm
confirm that the skeleton of the
Jørgensen–Hayashi catalyst has
been well embedded into the
JH-CPP network. Meanwhile,
the peaks at approximately 130
and 141 ppm indicate the suc-
Scheme 1. Rational design and synthesis of a chiral porous polymer (JH-CPP) embedded with Jørgensen–
Hayashi catalyst (JH) by the bottom-up strategy. The structural uniqueness of the JH catalyst as the functional
building block is depicted (top). Through the Co2(CO)8-mediated trimerization, the JH-CPP polymer could be
facilely synthesized from JH and the structural building block. The simulated local structure of JH-CPP
(bottom) shows the pore formation and the distribution of catalytic moieties (red). For clarity, all hydrogen
atoms were omitted.
tional building block and tetra(4-ethynylphenyl)metha-
ne[25,26b] as the structural building block (molar ratio of 1:1).
The bottom-up construction of JH-CPP was successfully
achieved within 10 min at 1158C through the Co2(CO)8-
mediated trimerization of the ethyne groups in the building
blocks. After cooling, the resulting dark precipitate was fil-
tered and washed thoroughly with ethanol, water, methanol,
and acetone to afford JH-CPP in 98% yield. The obtained
polymer is insoluble in all of the solvents tested, and is
stable up to 2808C under nitrogen atmosphere (TGA result
shown in Figure S1 in the Supporting Information). Powder
X-ray diffraction measurements indicated that the JH-CPP
polymer is amorphous in nature (Figure S2 in the Support-
ing Information). The SEM images showed that JH-CPP ap-
pears as aggregates of smaller particles with diameters rang-
ing from 50 to 100 nm (Figure S3 in the Supporting Informa-
tion).
cessful formation of benzene ring through the Co2(CO)8-
mediated trimerization of ethyne groups. The detailed as-
signments for 13C NMR signals are presented in Figure 2,
top. Additionally, elemental analysis on the nitrogen content
(0.96%) identified that the loading of the Jørgensen–Haya-
shi catalyst in JH-CPP is approximately 0.69 mmolgÀ1. All
of this information verified the bottom-up construction of
the chiral nanoporous polymer JH-CPP with the Jørgensen–
Hayashi catalyst embedded into the network.
The Michael addition reaction represents one of the most
À
powerful methods for the formation of C C bonds in organ-
ic synthesis. Significant progress[28] has been made recently
in achieving organocatalytic asymmetric Michael reactions
with a diverse combination of Michael donors and acceptors.
To evaluate the catalytic activity of JH-CPP as a robust
heterogeneous asymmetric organocatalyst, we accordingly
chose the enantioselective Michael addition of propanal to
(E)-4-chloro-b-nitrostyrene as a model reaction (Table 1).
The influence of different solvents on this reaction was first-
ly investigated and the results were summarized in Table 1.
The permanent porosity of JH-CPP was investigated by
nitrogen sorption measurements at 77 K. As shown in Fig-
ure 1a, JH-CPP displays a type-IV gas sorption isotherm
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Table 1. Screening the solvents for the asymmetric Michael addition re-
action catalyzed by JH-CPP.[a]
Entry
Solvent
t [h]
Yield [%][b]
syn/anti[c]
ee [%][d]
1
2
3
4
n-hexane
CH2Cl2
MeOH
H2O
EtOH
16
20
3
12
10
2
26
24
75
89
96
96
64
89:11
90:10
89:11
85:15
84:16
92:8
93
99
98
98
94
99
97
5
6
EtOH/H2O (1:1)
EtOH/H2O (1:1)
7[e]
24
78:22
[a] General condition: (E)-4-chloro-b-nitrostyrene (0.1 mmol), propanal
(1.0 mmol), JH-CPP (0.01 mmol), solvent (0.5 mL), benzoic acid
(0.1 mmol), RT. [b] Isolated yield after silica gel column chromatography.
[c] Determined by 1H NMR spectroscopy. [d] Determined by chiral
HPLC (Daicel chiral AD-H column). [e] No benzoic acid.
All of the solvents tested proved to be efficient for enantio-
selective control, providing the desired product with excel-
lent enantioselectivity (93–99% ee). However, the reaction
yield varied significantly. With n-hexane (Table 1, entry 1)
or CH2Cl2 (entry 2) as the solvent, low yield (24–26%) was
observed. On the contrary, high yields (75–96%) could be
achieved when MeOH, H2O, or EtOH was applied (Table 1,
entries 3–5). More strikingly, we found that the reaction pro-
ceeded much faster in EtOH/H2O (v/v=1:1) and gave the
desired product in 96% yield and high enantioselectivity
(99% ee) (Table 1, entry 6). The effect of benzoic acid on
the reaction was also examined. The reaction proceeded
much slower in the absence of benzoic acid, giving the prod-
uct in moderate yield (64%) and diastereoselectivity (d.r.
78:22) after 24 h (Table 1, entry 7). Finally, the optimized
conditions for the asymmetric Michael reaction of aldehydes
to nitroalkenes were chosen as: EtOH/H2O (v/v=1:1) as
the co-solvent, 10 mol% of JH-CPP as the heterogeneous
catalyst, in the presence of benzoic acid, and at ambient
temperature.
Figure 1. a) Nitrogen sorption isotherm of JH-CPP. b) Pore size distribu-
tion (PSD) for JH-CPP, calculated with non-local density functional
theory (NLDFT).
The substrate scope of the asymmetric Michael reaction
catalyzed by JH-CPP in EtOH/H2O was examined with a
variety of aldehydes and nitroalkenes (Table 2). Nitroal-
kenes with either an electron-withdrawing or -donating sub-
stituent on the benzene ring were employed (Table 2, en-
tries 1–6) and so was the heteroaromatic nitroalkene
(Table 2, entry 7). The reaction was complete within 5 h,
giving the corresponding products in good to excellent
yields (67–99%) and high enantioselectivities (93–99% ee),
together with high diastereoselectivity (d.r. of 74:26 to 92:8).
The nitroalkene with di-substitution on the benzene ring
(Table 2, entry 8) or the aldehydes with elongated chains
(Table 2, entries 9 and 10) also gave satisfactory results, al-
though with slightly increased reaction time (6–16 h). For
the purpose of comparison, we also investigated the catalytic
performance of the homogeneous JH catalyst in the Michael
Figure 2. Solid-state 13C CP/MAS NMR spectrum of JH-CPP. The assign-
ments for the 13C MAS NMR signals are indicated (top).
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W. Wang et al.
Table 2. Investigating the substrate scope of the asymmetric Michael ad-
addition reaction under the same reaction conditions, and
the results are listed in parentheses in Table 2 (entries 2, 3,
and 7). It can be seen that the efficiency of JH-CPP poly-
mer compares well to that of the homogeneous JH catalyst.
These results identified that the JH-CPP nanoporous poly-
mer works as a highly efficient heterogeneous organocata-
lyst for the asymmetric Michael addition reaction.
Next, we examined the recyclability and catalytic stability
of the JH-CPP catalyst (Table S1 in the Supporting Infor-
mation). The recycling experiment was performed by recov-
ering the JH-CPP catalyst by using the centrifugation
method. The recovered JH-CPP catalyst was washed with
EtOAc to remove the residual product and simply dried
before reuse. As shown in Figure 3, the JH-CPP catalyst
dition reaction catalyzed by JH-CPP.[a]
Entry
1
Product
t [h]
Yield [%][b]
99
syn/anti[c]
ee [%][d]
1.5
92:8
98
2
(3.5
96
91
92:8
92:8
99
97)[e]
2
3
3
(3.5
88
91
91:9
86:14
98
>99)[e]
4
5
1.5
3.5
98
84
90:10
74:26
97
94
6
7
8
5
67
82:18
93
Figure 3. Recycling experiment of JH-CPP for the asymmetric Michael
addition reaction of (E)-4-chloro-b-nitrostyrene and propanal.
1
(1
98
99
88:12
76:24
95
96)[e]
can be reused at least four times without the loss of enantio-
selectivity (97 to 99% ee) and diastereoselectivity (d.r. 92:8
to 88:12). However, the reaction yield decreased to 51% in
the third recycling experiment, which could be due to the
partial blocking[20c] of the polymeric nanopores. We found
that the BET surface area of JH-CPP had decreased to
578 m2 gÀ1 after the fourth recycle use (Figure S4 in the Sup-
porting Information). The 13C CP/MAS NMR spectrum re-
corded showed that the recycled JH-CPP catalyst still main-
tained its rigid structure (Figure S5 in the Supporting Infor-
mation). However, some species could have been occluded
inside the polymeric nanopores as evidenced by the in-
creased intensity of signals at d=130 ppm and by the ap-
pearance of new signals in the high-field region of d=0 to
50 ppm (Figure S5 in the Supporting Information). Very re-
cently, Blackmond and co-workers[29] performed a mechanis-
tic study on the homogeneously organocatalyzed reaction of
linear aldehydes to nitroalkenes in the presence of the Jør-
gensen–Hayashi catalyst. They identified a bulky cyclobu-
tane intermediate formed as the catalyst resting state before
the rate-determining step.[29] As implied by our 13C CP/MAS
NMR results (Figure S5 in the Supporting Information),
16
6
75
86
88:12
95:5
96
97
9
10
12
85
97:3
97
[a] General condition: nitroalkene (0.1 mmol), aldehyde (1.0 mmol), JH-
CPP (0.01 mmol), EtOH/H2O (0.5 mL), benzoic acid (0.1 mmol), RT.
[b] Isolated yield after silica gel column chromatography. [c] Determined
by 1H NMR spectroscopy. [d] Determined by chiral HPLC and the abso-
lute configuration of reaction products were determined according to ref-
erence [3]. [e] The homogeneous JH catalyst (10 mol%) was applied for
the purpose of comparison.
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similar species covalently bonded to the JH-CPP polymeric
network may also exist in the recycling experiments. In con-
trast to the homogeneous case in which the “parasitic” cata-
lytic intermediate could undergo further transformation, the
inclusion of bulky intermediates inside the nanopores (espe-
cially the micropores) would slow down the reaction due to
the decreased mass transport rate. In this context, construc-
tion of polymeric catalysts with abundant mesopores may be
of great importance for highly efficient catalysis.[20j] On the
other hand, Blackmond and co-workers[29] revealed that the
formation of the cyclobutane intermediate benefits the
maintenance of high stereoselectivity, which may also fit in
our case. Additionally, the nitrogen content of the JH-CPP
after the fourth recycle use increased to 1.18%, which might
also imply the existence of the NO2-containing cyclobutane
intermediate as suggested by Blackmond and co-workers.[29]
In conclusion, one of the most versatile organocatalysts,
that is, the Jørgensen–Hayashi catalyst, has been successfully
embedded into a nanoporous polymer JH-CPP through a
bottom-up strategy. The high BET surface area (881 m2 gÀ1),
wide openings, and interconnected pores of JH-CPP ensur-
ed its excellent catalytic activity by increasing the accessibil-
ity of catalytic sites and facilitating the mass transport proc-
ess. Catalyzed by the JH-CPP catalyst, the asymmetric Mi-
chael addition of aldehydes to nitroalkenes gives the desired
products in good to excellent yield (67–99%), high enantio-
selectivity (93–99% ee) and high diastereoselectivity (d.r. of
74:26 to 97:3). The JH-CPP catalyst could be reused at least
for four times without loss of enantioselectivity (97–99% ee)
and diastereoselectivity (d.r. 92:8 to 88:12). We believe that
JH-CPP may act as a promising heterogeneous organocata-
lyst applicable to a variety of asymmetric organocatalyzed
reactions. Moreover, the bottom-up strategy and the suc-
cessful example presented in this contribution sheds new
light on the development of heterogeneous organocatalysis,
the further progress of which may eventually bring chiral
porous materials into industrial applications.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (No. 21172103), the Key Grant Project of the Chinese Ministry of
Education (No. 309028), and the 111 Project.
Keywords: asymmetric catalysis · heterogeneous catalysis ·
organocatalysis · Michael addition · supported catalysts
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Received: March 6, 2012
Published online: && &&, 0000
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www.chemeurj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!

Heterogeneous Asymmetric Organocatalysis
COMMUNICATION
Heterogeneous Organocatalysis
C. A. Wang, Z. K. Zhang, T. Yue,
Y. L. Sun, L. Wang, W. D. Wang,
Y. Zhang, C. Liu, W. Wang* &&&& — &&&&
“Bottom-Up” Embedding of the
Jørgensen–Hayashi Catalyst into a
Chiral Porous Polymer for Highly Effi-
cient Heterogeneous Asymmetric
Organocatalysis
The only way is up! “Bottom-up” con-
struction of a robust chiral porous pol-
ymer (JH-CPP) embedded with the
Jørgensen–Hayashi catalyst (JH) has
been successfully achieved for highly
efficient heterogeneous organocataly-
sis. The high BET surface area, wide
openings and interconnected nano-
pores of JH-CPP increase the accessi-
bility of catalytic sites and as such the
catalyst shows excellent activity in cat-
alyzing the asymmetric Michael addi-
tion reaction (see scheme).
The so-called “Birdꢀs Nest”…
… (the framework of the Beijing
National Stadium as depicted on
the cover), bears a resemblance to
the rigid porous catalyst
constructed for highly efficient
heterogeneous asymmetric organo-
catalysis by W. Wang et al. in their
Communication on page && ff.
The chiral porous polymer
containing the Jørgensen–Hayashi
catalyst shows excellent activity in
the asymmetric Michael addition
reaction.
Chem. Eur. J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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ÞÞ
These are not the final page numbers!