The Use of Porous Palladium(II)-polyimine in Cooperatively- catalyzed Highly Enantioselective Cascade Transformations

Article abstract of DOI:10.1002/adsc.201500100

Porous organic polymers have prospects as functional substrates for catalysis, with quite different molecular properties from inorganic substrates. Here we disclose for the first time that porous palladium(II)-polyimines are excellent catalysts for cooper

Full text of DOI:10.1002/adsc.201500100

UPDATES
DOI: 10.1002/adsc.201500100
The Use of Porous Palladium(II)-polyimine in Cooperatively-
catalyzed Highly Enantioselective Cascade Transformations
a,b
a,c
d
d
Chao Xu, Luca Deiana, Samson Afewerki, Celia Incerti-Pradillos,
d
a,b
a,c,d,
a,b,
Oscar Cꢀrdova, Peng Guo, Armando Cꢀrdova, * and Niklas Hedin *
Berzelii Center EXSELENT on Porous Materials, Stockholm University, Stockholm, SE-10691, Sweden
a
Fax : (+46)-8152187; phone: (+46)-8162417; e-mail: niklas.hedin@mmk.su.se
Department of Materials and Environmental Chemistry, Arrhenius Laboratory Stockholm University, Stockholm
b
SE-10691, Sweden
c
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm SE-10691, Sweden
Department of Natural Sciences, Mid Sweden University, Sundsvall SE-85170, Sweden
d
Fax : (+46)-60148510; phone: (+46)-707415178; e-mail: acordova@organ.su.se or armando.cordova@miun.se
Received: February 1, 2015; Revised: March 13, 2015; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500100.
Abstract: Porous organic polymers have prospects
as functional substrates for catalysis, with quite dif-
ferent molecular properties from inorganic sub-
strates. Here we disclose for the first time that
porous palladium(II)-polyimines are excellent cata-
lysts for cooperatively catalyzed and enantioselec-
tive cascade reactions. In synergy with a chiral
amine co-catalyst, polysubstituted cyclopentenes
and spirocyclic oxindoles, including the all-carbon
quaternary stereocenter, were synthesized in high
yields. High diastereo- and enantioselectivities were
achieved for these dynamic kinetic asymmetric
transformations (DYKAT) of enals with propargylic
nucleophiles.
for coupling, cyclization and hydrogenation reac-
[
5]
2+
tions. Ding et al. reported on a Pd based catalyst
that was heterogenized on a crystalline porous polyi-
mine, which was effective for Suzuki–Miyaura cou-
[
6]
pling reactions. Amorphous porous polyimines, on
the other hand, may have a larger potential to form
complexes with noble metal ions than most crystalline
polyimines. Their broad distributions of N…N distan-
ces and the significant amount of –NH end groups
2
will contribute to an enhanced tendency to form com-
[
7]
plexes with noble metal ions.
Porous organic substrates have only recently started
being used for asymmetric catalysis, even though
asymmetric synthesis of small molecules is of the
utmost importance for life science research and the
[
8]
pharmaceutical industry. The application of cascade
Keywords: cascade reaction; cooperative catalysis;
enantioselective synthesis; heterogeneous catalysis;
palladium; porous organic polymers
[
9,10]
transformations is growing.
It is an eco-friendly
approach to create multiple CꢀC and Cꢀhetero atom
bonds in one-pot, which reduces the generation of
waste and excess use of solvents in comparison to tra-
[
11]
ditional organic step-by-step synthesis.
The devel-
opment of asymmetric versions for the generation of
Porous polymers built from pure organic building several contiguous stereocenters in a highly enantio-
blocks can display ultra-high surface areas and micro- selective fashion is still a major challenge. Particularly
[
1]
[12]
pores (pores <2 nm) due to cross-links or disor- difficult is the synthesis of quaternary stereocenters.
[
2]
dered interpenetrations among the polymer chains.
Consequently, it is relevant to investigate such even-
Their covalent and often aromatic nature make them tual advantages for porous organic polymers as sub-
[
3]
thermally and chemically stable. Only quite recently strates for catalyzed asymmetric cascade transforma-
have such polymers started to be studied as functional tions. Guided by our previous work on porous organic
[
7d]
and heterogeneous catalysts for single bond-forming polymers,
transformations.
we envisioned the synthesis of a Lewis
[4]
2+
acidic (Pd ) based porous polyimine polymer that we
Porous polyimines are well suited as supports for could investigate as a catalyst for the dynamic kinetic
catalysis as their imine groups can form complexes asymmetric transformations (DYKAT) of enals 1 with
1
[13,14]
with metal ions. The imines are well suited for metal propargylic nucleophiles 2 (E ¼
6
E )
in coopera-
2
+
2+
3+
3+
[13]
ions catalysts (Pd , Pt , Ru , Ir ) that can be used tion with an amine catalyst (Scheme 1a). This reac-
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Chao Xu et al.
UPDATES
1
Scheme 1. (a) Possible DYKAT between enals 1 and propargylic nucleophiles 2 in the presence of E and E =electron with-
[14]
2+
drawing group. (b) Synthesis route of the porous polyimine (PP-1), and the catalyst Pd /PP-1. (An idealized structure of
PP-1 only.)
tion proceeded via a reversible Michael/carbocycliza- covered by a workup procedure (see experimental
tion/isomerization cascade pathway, which could theo- section).
2+
retically generate four possible stereoisomers of cy-
The molecular conformations of PP-1 and Pd /PP-
clopentenes 4 via Michael intermediates 3. However, 1 were studied by solid state nuclear magnetic reso-
[
13]
in cooperation with heterogeneous or homogeneous nance (NMR), infrared (IR), and X-ray photoelectron
[14]
13
1
metal /chiral amine (5) catalyst systems a predomi- (XPS) spectroscopy (Figure 1). The solid state C{ H}
nant stereoisomer of the corresponding poly-function- CPMAS NMR spectrum of PP-1 displays characteris-
alized product 4 containing a quaternary stereocenter, tic peaks for carbon atoms in imine and free aldehyde
can be assembled in high yield, diastereomeric ratio groups at chemical shifts of 163 and 192 ppm. The sig-
(
dr) and enantiometric ratio (er).
Here, we show for the first time that porous Pd - nary aromatic carbon atoms, respectively, while those
polyimines are excellent co-catalysts for cooperatively at 16 ppm were assigned to –S–R based decomposi-
nals at 128 and 138 ppm belong to secondary and ter-
2+
[
15]
catalyzed enantioselective cascade reactions. Our ef- tion products of DMSO
(additional signatures of
forts began with the porous polyimine substrate, PP-1. the decomposition products appear to be convoluted
It was synthesized through the condensation of 1,3,5- with the side band intensities at ~35 ppm). The de-
tris(4-aminophenyl)benzene and 1,3,5-benzenetricar- composition products of DMSO are also detected by
ꢀ1
boxaldehyde in refluxing DMSO (Scheme 1b), under an IR band at ~1035 cm , see Figure 1a–b. The IR
dynamic equilibrium and the release of water. An un- spectrum shows a strong band for the imine stretching
ꢀ
1
equal amine-to-aldehyde ratio of 3:2 was used, and (C=N) band at a frequency of 1669 cm . A high-reso-
2+
the PP-1 displayed a narrow distribution of micro- lution XPS spectrum of Pd /PP-1 shows the charac-
pores and a broad distribution of mesopores. The cat- teristic doublet in the Pd 3d region. The peak at
2
+
2+
2+
alyst Pd /PP-1 was formed by complexation of Pd
337.9 eV corresponded to 3d5/2 and belongs to Pd .
2+
with the imine and possibly amine groups of PP-1. Similar 3d5/2 XPS bands were observed for Pd in Pd/
For the complexation, Pd(OAc) was added to a sus- COF-LZU1 (337.7 eV) and a model complex of Pd/
2
2+
[6]
pension of PP-1 in CH Cl , and the Pd /PP-1 was re- Phen (337.8 eV). In contrast, for free Pd(OAc) that
2
2
2
2
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UPDATES
The Use of Porous Palladium(II)-polyimine
Figure 2. Nitrogen adsorption (solid) and desorption
empty) isotherms of the porous polyimine PP-1 (squares)
(
2+
and the catalyst Pd /PP-1 (circles) at 77 K. Inset shows
2+
pore size distribution of PP-1 (upper line) and Pd /PP-
(lower line) analyzed on the N adsorption isotherms with
1
2
DFT method.
distributed mesopores. The large hystereses in be-
tween adsorption and desorption in Figure 2 corre-
[
18]
spond to “swelling”. It is still being investigated if
such “swelling” relates to the degree of cross-linking,
a somewhat elastic expansion of the polymer, or a re-
[
19]
1
3
1
stricted access to small pores. Both swelling of the
Figure 1. (a) Solid state C{ H} nuclear magnetic resonance
spectrum of the porous polyimine (PP-1), side bands denot- polymer and the presence of mesopores can help to
ed by (*); (b) infrared spectrum of PP-1; (c) high-resolution accommodate relatively large catalysts, reactants and
2+
X-ray photoelectron spectrum (Pd 3d) of the catalyst Pd / products, and can contribute to the rapid mass trans-
PP-1.
port of reactants and products.
The mesopores of Pd /PP-1 were visible by trans-
mission electron microscopy (TEM) (Figure 3), and
2+
band was detected at 338.4 eV. A shoulder peak at display the character of intraparticle based and disor-
3
36.0 ev indicates the existence of small relative dered mesopores, which are quite different compared
0
2+
[20]
amount of Pd (9.8w%) in Pd /PP-1 (Figure S2), with those in ordered mesoporous materials.
which is quite common in such catalysts.
In
general, disordered mesopores are difficult to detect
The porosities of the PP-1 and Pd /PP-1 were stud- by TEM, with some previously reported TEM images
[
16]
2
+
[
3c]
ied by N sorption experiments. Both compositions not clearly displaying the mesopores; here, the con-
2
showed both (ultra)micro- and mesopores, which is trast variations in the images agree well with the pore
indicative of highly cross-linked and tight interpene- sizes deduced from the N adsorption data.
2
trated structures. The PP-1 had a specific surface area
2
ꢀ1
2
ꢀ1
of 256 m g , which was reduced to 92 m g for the
2+
Pd /PP-1. The large reduction indicated a change in
the polymer conformation as the Pd /PP-1 contained
.3 wt% Pd. The adsorption and desorption isotherms
2+
2
2+
of N on PP-1 and Pd /PP-1, in Figure 2 show distinct
2
N uptake at low partial pressures belonging to micro-
2
pores. The desorption isotherms display a step at
a partial pressure of P/P = ~0.45–0.5, indicative of
0
partially blocked mesopores. This cavitation based un-
loading occurred at lower relative pressures (0.31–
[
17]
0.36) for Ar (Figure S1, SI).
The corresponding
pore size distribution shows micropores in PP-1 with Figure 3. Transmission electron microscopy images of (a)
2
+
pore size centered at 0.7 nm and 1.3 nm, and broadly PP-1 and (b) Pd /PP-1.
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Chao Xu et al.
UPDATES
2+
After establishing the synthesis and characteriza- Table 1. Scope of use of a heterogeneous Pd /PP-1/chiral
2+
amine catalyst to react enals with propargylic nucleophiles
into carbocycles.
tion of Pd /PP-1 in detail, we began to investigate if
it could act as a catalyst for the synthesis of various
carbocycles (Scheme 1a). Thus, a catalyst system of
2+
Pd /PP-1 and chiral amine-based co-catalyst 5 was
tested for the DYKAT reactions between enals 1 and
propargylic nucleophile 2 that if successful could give
the corresponding carbocycles 4 with an all-carbon
stereocenter via Michael intermediates 3. An initial
screening of the conditions (Table S1, SI), revealed
that highly enantioselective cascade reactions were
possible using dynamic cascade catalysis in toluene
2+
with the catalytic system (Pd /PP-1/chiral amine).
The co-catalytic reaction converted cinnamic alde-
hyde 1a to 4a in an 85% yield with a diastereomeric
ratio (dr) of 95:5 and an enantiometric ratio (er) of
2+
9
7.5:2.5. To form 4 both the Pd /PP-1 and the chiral
amine 5 had to be present, demonstrating the synergy
achieved by the two catalysts for the cascade se-
quence.
2+
The catalytic system Pd /PP-1/chiral amine was
further investigated for the dynamic cascade reactions
for a set of enals 1 in toluene (Table 1). These Mi-
chael–carbocyclization reactions were highly enantio-
selective. The corresponding cyclopentenes 4 were
isolated in high yields with up to 97:3 dr and 99.5:0.5
er. Moreover, having electron-donating or electron-
withdrawing groups on the b-aryl-substituted 1 did
not affect the efficiency or stereoselectivity of the re-
actions. The spirocyclic oxindole structural motif 7,
with an all carbon quaternary stereocenter, is a valua-
ble structural motif present in several natural prod-
[
21]
2+
ucts and pharmaceuticals.
With the Pd /PP-1, we
achieved similar (or better), as compared with amine-
2+ [13]
modified silica supported Pd , enantioselective for-
mation of such spirocyclic oxindoles 7 (up to>
99.5:0.5 er) by the conjugate/carbocyclization cascade
transformation between enals 1 and 6 (Scheme 2).
2+
[
a]
The cascade reactions with Pd /PP-1 were signifi-
Isolated yield of pure compound 4.
2+
[b]
1
cantly faster than with Pd supported on aminoprop-
yl-modified silica of the mesocellular foam type, as
Determined by H NMR.
[c]
Determined by chiral-phase HPLC analysis.
[d]
1
[13a]
Reaction performed at 48C.
determined by H-NMR.
The products 4 also
showed slightly higher dr and er. The absolute stereo-
chemistry of the cyclopentenes 4 and the spirocyclic
2+
oxindoles 7 was determined by comparing them with 1 was used for the recycling experiments). No Pd
[14a,22]
the literature.
Performing the reactions with leaching was observed as determined by elemental
a chiral amine 5 provided carbocycles (1R,2R)-4 (R= analysis. (The elemental analysis was performed on
aryl) with an R configuration at C-1 and C-2, while the filtrate after hot filtration and after completion of
the intermediate Michael adducts 3 were nearly race- the reaction. It showed very low Pd contents of 7.5
2+
mic in the presence of the Pd /PP-1 co-catalyst. and 15.1 ppm in the filtrates, respectively. The back-
Thus, the co-catalytic reactions proceed via the ground Pd content was 9 ppm as determined for
[
23]
2+
DYKAT mechanism. An important aspect in heter- a sample where no Pd /PP-1 catalyst was added).
ogeneous catalysis is the recovery of the solid catalyst. In summary, we showed for the first time that
2+
The Pd /PP-1 catalyst showed excellent recyclability porous organic polymers can successively be applied
with respect to the yield of product 4a, and the enan- to heterogeneous catalysis for asymmetric cascade re-
2+
tioselectivity of the cascade sequence was not signifi- actions. First, the Lewis acidic catalyst Pd /PP-1 was
2+
2+
cantly affected (Table S2, SI, 2.2 mol% of Pd /PP- synthesized directly by complexation. Next, Pd /PP-
4
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UPDATES
The Use of Porous Palladium(II)-polyimine
a suspension of PP-1 (100 mg) in CH Cl (12 mL) under ni-
2
2
trogen, and the reacting mixture was stirred for 24 h. Next,
the reaction mixture was transferred to a centrifuge vial
(
45 mL) and centrifuged 3 times with CH Cl (40 mL). The
2 2
solid was purified by Soxhlex extraction with CH Cl2 at
2
a temperature of 708C for 24 h and subsequently dried
under dynamic vacuum conditions.
General procedure for the combined transition metal/
chiral amine catalytic enantioselective reaction using
methyl propargylcyanoacetate
Scheme 2. Cascade synthesis of spirocyclic oxindoles 7.
An oven-dried microwave vial equipped with a magnetic stir
1
was shown to be an excellent heterogeneous catalyst bar was charged with methyl propargylcyanoacetate
2+
for the DYKATs between enals and propargylic nu- (16.1 mg, 0.12 mmol, 1.2 equiv) and Pd /PP-1 (5 mg,
cleophiles together with a chiral amine co-catalyst. 1.1 mol% or 2.5 mg, 0.55 mol%), followed by addition of
2+
toluene (0.100 mL) and the resulting mixture was stirred at
room temperature for 5 min. In parallel to the above proce-
dure, an oven-dried vial was charged with the aldehyde
The Pd /PP-1/chiral amine system provided an excel-
lent catalysis platform for the synthesis of highly func-
tionalized carbocycles and spirocyclic oxindoles, in-
cluding the all-carbon quaternary center, in high yield
with up to 97:3 dr and 99.5:0.5 er. It also exhibited
a higher reactivity in comparison to systems based on
amine-modified mesocellular silica particles. These re-
(
2
0.1 mmol, 1.0 equiv), organocatalyst (6.5 mg, 0.02 mmol,
0 mol%) and followed by addition of toluene (0.150 mL),
after stirring at room temperature for additional 5 min, the
resulting mixture was transferred to the vial containing the
mixture of palladium catalyst and methyl propargylcyanoa-
sults indicate that metal-bound polyimine based cetate via a syringe. (Total volume of toluene=0.250 mL,
2+
porous polymers (e. g. Pd /PP-1 and Pd/COF- final concentration=0.8m to aldehyde). The reaction was
[6]
LZU1 ) should be widely useful catalysts and co-cat- stirred for the time shown in the table. The conversions and
1
diastereomeric ratios were monitored by H NMR analysis
of the crude mixture. Upon completion, the mixture was di-
rectly subjected to flash chromatography on silica (pentane/
EtOAc) affording the pure products.
alysts for various cascade transformations involving
CꢀC bond formation. We expect that mesoporosity,
and the ability for the porous polymer to swell will be
important properties for the use of nanoporous poly-
mers as a functional catalyst. Here they could serve
as a modular bridge between heterogeneous and ho-
mogeneous catalysis. In particular, applications to-
Methyl (1R,2R)-1-cyano-3-formyl-4-methyl-2-phenyl-cy-
1
clopent-3-enecarboxylate (4a): oil; H NMR (400 MHz,
CDCl ): d 9.92 (s, 1H), 7.38–7.32 (m, 3H), 7.17–7.15 (m,
3
2
H), 4.72 (bs, 1H), 3.89 (s, 3H), 3.41 (d, J=14.8 Hz, 1H),
wards integrated heterogeneous metal/chiral amine 3.26 (dt, J=12.4 Hz, Jꢀ=1.2 Hz, 1H), 2.33 (d, J=0.8 Hz,
[
13b]
13
multiple relay catalysis could be expected.
3H); C NMR (100 MHz, CDCl
36.6, 129.1, 128.7, 128.0, 117.4, 58.4, 54.4, 51.7, 47.9, 14.3;
HRMS (ESI) : calcd for [M+Na] (C H NO ) requires m/z
3
): 186.2, 168.8, 157.8, 136.8,
1
1
6
15
3
2
5
2
92.0944, found 292.0946; [a] =ꢀ68.2 (c=1.0 CHCl ). The
D
3
Experimental Section
enantiomeric excess was determined by HPLC analysis in
comparison with authentic racemic material (ODH-column,
Synthesis of PP-1
ꢀ1
n-hexane/iPrOH=85/15, l=210 nm, 1.0 mLmin ) t (major
r
1,3,5-Tris(4-aminophenyl)benzene (0.375 mmol, 132 mg) was
enantiomer)=16.01 min, t (minor enantiomer)=24.4 min.
r
dissolved in 5 mL of dimethyl sulfoxide (DMSO) and
formed a yellow solution. A colorless solution of 1,3,5-ben-
zenetricarboxaldehyde (0.25 mmol, 41 mg) in 5 mL of
DMSO were prepared, which was added drop-wise to the
amine solution at a temperature of 508C. A pale yellow so-
lution formed. This solution was heated at a temperature of
General procedure for the combined transition metal/
chiral amine catalytic enantioselective reaction using
propargyloxindole
An oven-dried microwave vial equipped with a magnetic stir
bar was charged with propargyloxindole (20.5 mg,
1208C for 12 h and subsequently refluxed at a temperature
of 2008C under stirring for another 3 days. Yellow precipi-
tates formed at 1208C, which turned brown during the
reflux. The brown precipitates were filtered off, and repeat-
edly washed with methanol or tetrahydrofuran until the fil-
trates were colorless. The resulting precipitates were dried
0
2
.12 mmol, 1.2 equiv), PhCO H (2.4 mg, 0.02 mmol,
0 mol%) and Pd /PP-1 (5 mg, 1.1 mol%), followed by ad-
2
2+
dition of toluene (0.100 mL) and the resulting mixture was
stirred at room temperature for 5 min. In parallel to the
above procedure, an oven-dried vial was charged with the
aldehyde (0.1 mmol, 1.0 equiv), organocatalyst (6.5 mg,
at a temperature of 2008C under a N atmosphere.
2
0
.02 mmol, 20 mol%) and followed by addition of toluene
(0.150 mL), after stirring at room temperature for additional
min, the resulting mixture was transferred to the vial con-
taining the mixture of palladium catalyst and propargylcya-
noacetate via syringe. (Total volume of toluene=
2+
Synthesis of Pd /PP-1
5
The coarse particles of PP-1 were ground with a mortar for
2
0 min into a fine powder. Pd(OAc) (100 mg) was added to
a
2
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Chao Xu et al.
UPDATES
0
.250 mL, final concentration=0.8m to aldehyde). The reac-
[5] K. C. Gupta, A. K. Sutar, Coord. Chem. Rev. 2008, 252,
1420–1450.
[6] S.-Y. Ding, J. Gao, Q. Wang, Y. Zhang, W.-G. Song, C.-
Y. Su, W. Wang, J. Am. Chem. Soc. 2011, 133, 19816–
19822.
tion was stirred for the time shown in the table. The conver-
sions and diastereomeric ratio were monitored by H NMR
analysis of the crude mixture. Upon completion, the mixture
was directly subjected to flash chromatography on silica
1
(
pentane/EtOAc) affording the pure products.
1R,2R)-2-(4-chlorophenyl)-4-methyl-2’-oxospiro[cyclo-
[7] a) E. Verde-Sesto, E. M. Maya, ꢂ. E. Lozano, J. G. de
La Campa, F. Sꢃnchez, M. Iglesias, J. Mater. Chem.
2012, 22, 24637–24643; b) P. Pandey, A. P. Katsoulidis,
I. Eryazici, Y. Wu, M. G. Kanatzidis, S. T. Nguyen,
Chem. Mater. 2010, 22, 4974–4979; c) Y. Zhu, H. Long,
W. Zhang, Chem. Mater. 2013, 25, 1630–1635; d) C. Xu,
N. Hedin, J. Mater. Chem. A 2013, 1, 3406–3414.
[8] H. Yamamoto, E. Carreira (Eds.), Comprehensive Chir-
ality, Elsevier, Oxford, 2012.
(
pent[3]ene-1,3’-indoline]-3-carbaldehyde (7d): Yellow oil;
IR (neat): nmax 3017 (w), 2923 (w), 1707 (m), 1666 (m), 1620
(
(
5
m), 1489 (m), 1471 (m), 1378 (w), 1335 (m), 1215 (w), 1090
w), 1015 (w), 843 (w), 746 (s), 667 (m), 592 (w), 569 (w),
ꢀ
1
1
24 (w), 492 (w) cm ; H NMR (500 MHz, CDCl ): d 10.08
3
(
3
(
s, 1H), 8.05 (br s, 1H), 7.10–7.01 (m, 3H), 6.80–6.72 (m,
H), 6.69 (t, J=7.6 Hz, 1H), 6.33 (d, J=7.6 Hz, 1H), 4.61
br s, 1H), 3.09 (d, J=18.9 Hz, 1H), 2.94 (d, J=18.8 Hz,
[
9] a) L. F. Tietze, Chem. Rev. 1996, 96, 115–136; b) K. C.
Nicolaou, D. J. Edmonds, P. G. Bulger, Angew. Chem.
1
3
1
1
1
:
H), 2.42 (s, 3H); C NMR (125.8 MHz, CDCl ): 187.1,
3
82.2, 161.6, 140.2, 137.5, 136.6, 132.9, 130.4, 129.5, 128.4,
28.3, 125.0, 122.2, 109.6, 57.9, 56.5, 48.9, 14.9; HRMS (ESI)
2
7
006, 118, 7292–7344; Angew. Chem. Int. Ed. 2006, 45,
134–7186; c) H.-C. Guo, J.-A. Ma, Angew. Chem.
calcd for [M+Na] (C H ClNO ) requires m/z 360.0762,
2
0
16
2
2006, 118, 362–375; Angew. Chem. Int. Ed. 2006, 45,
354–366.
2
5
found 360.0772; [a] =ꢀ99.8 (c=1, CHCl ). The enantio-
D
3
meric excess was determined by HPLC analysis in compari-
[
[
10] a) L. F. Tietze, A. D u˝ rfert, in: Catalytic Asymmetric
Conjugate Reactions (Ed.: A. Cꢀrdova), Wiley-VCH,
Weinheim, 2010, Ch. 8, p. 321; b) X. Yu, W. Wang, Org.
Biomol. Chem. 2008, 6, 2037–2046; c) D. Enders, C.
Grondal, M. R. M. H u˝ ttl, Angew. Chem. 2007, 119,
son with authentic racemic material (ODH-column, n-
hexane/iPrOH=80/20, l=210 nm, 1.0 mLmin ) t (major
enantiomer)=27.4 min, t (minor enantiomer)=18.7 min.
ꢀ
1
r
r
1
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This work was financially supported by the Berzelii Center
EXSELENT funded by VR and VINNOVA. Prof. Xiaodong
Zou is thanked for discussions on TEM microscopy. Marie
Ernstsson is thanked for XPS analyses. N.H. thanks the
Swedish Research Council and the Knut and Alice Wallen-
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The Use of Porous Palladium(II)-polyimine in
Cooperatively-catalyzed Highly Enantioselective Cascade
Transformations
Adv. Synth. Catal. 2015, 357, 1 – 8
Chao Xu, Luca Deiana, Samson Afewerki,
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