Heterogeneous Chiral Diene-Rh Complexes for Asymmetric Arylation of α,β-Unsaturated Carbonyl Compounds, Nitroalkenes, and Imines

Article abstract of DOI:10.1002/adsc.201900526

A chiral diene ligand with tertiary alkyl amine-derived secondary amide moiety was immobilized on cross-linked polystyrene (PS) by radical polymerization, which was combined with Rh to form heterogeneous chiral Rh complexes (PS-diene Rh?Cl). PS-diene Rh?Cl catalyzed asymmetric arylation reactions of α,β-unsaturated carbonyl compounds (ketones, esters, and amides), nitroalkenes, and imines afforded the desired products in high yields with excellent enantioselectivities. PS-diene Rh?Cl is stable in air, can be stored for several months, and can be reused more than 10 times without any reduction of either yield or enantioselectivity. We also developed a method of activation of PS-diene Rh?Cl to generate more active species. (Figure presented.).

Full text of DOI:10.1002/adsc.201900526

Title: Heterogeneous Chiral Diene-Rh Complexes for Asymmetric
Arylation of α,β-Unsaturated Carbonyl Compounds, Nitroalkenes,
and Imines
Authors: Shu Kobayashi, Tatsuya Kuremoto, and Tomohiro Yasukawa
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900526
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201900526
Heterogeneous Chiral Diene-Rh Complexes for Asymmetric
Arylation of α,β-Unsaturated Carbonyl Compounds,
Nitroalkenes, and Imines
Tatsuya Kuremoto,a Tomohiro Yasukawaa and Shū Kobayashia,*
a
Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)
E-mail: shu_kobayashi@chem.s.u-tokyo.ac.jp
In the memory of late Professor Teruaki Mukaiyama
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))
for both chiral Rh homogeneous complexes and chiral
Rh heterogeneous nanoparticle systems, both of which
show outstanding reactivities and enantioselectivities
in asymmetric 1,4-addition and 1,2-addition reactions
of a wide variety of substrates.[12-16] Considering the
value of the precious metal and the ligand, recovery
and reuse of both components has a high impact in
synthetic organic chemistry. There are several reports
of immobilization of Rh complexes with chiral
phosphine and diene ligands;[17-22] however, phosphine
ligands are prone to rapid oxidation under air, which
prevents facile recovery and reuse. On the other hand,
Lin et al. reported that immobilization of a diene Rh
complex could be achieved on a metal-organic
framework.[21] Very recently, Uozumi et al. succeeded
in the immobilization of a diene Rh complex on
polystyrene−poly(ethylene glycol).[22] However, none
of the catalysts have high catalytic efficiency or
display broad substrate scope with high
enantioselectivities for reactions of simple ,-
unsaturated carbonyl compounds, heteroarenes, and
nitroalkenes. Therefore, the development of highly
active heterogeneous catalysts that show wide
substrate generality for asymmetric arylation reactions
is desired.
Abstract. A chiral diene ligand with tertiary alkyl amine-
derived secondary amide moiety was immobilized on
cross-linked polystyrene (PS) by radical polymerization,
which was combined with Rh to form heterogeneous chiral
Rh complexes (PS-diene Rh−Cl). PS-diene Rh−Cl
catalyzed asymmetric arylation reactions of α,β-
unsaturated carbonyl compounds (ketones, esters, and
amides), nitroalkenes, and imines afforded the desired
products in high yields with excellent enantioselectivities.
PS-diene Rh−Cl is stable in air, can be stored for several
months, and can be reused more than 10 times without any
reduction of either yield or enantioselectivity. We also
developed a method of activation of PS-diene Rh−Cl to
generate more active species.
Keywords: heterogeneous catalyst; asymmetric 1,4-
addition; chiral diene; Rh catalyst; flow reaction
The development of heterogeneous chiral catalysts for
asymmetric C−C bond-forming reactions is among the
most important subjects in modern chemistry. Here,
precious chiral resources can be effectively utilized to
construct chiral skeletons of target molecules.[1-2] Not
only their ease of recovery and reuse, but their
potential application in continuous-flow reactions
using columns packed with heterogeneous catalysts
are attracting much attention as environmentally
benign, safe, and efficient systems.[3-5]
Here, we describe chiral diene ligand-immobilized
heterogeneous Rh catalysts for asymmetric arylation
reactions. A broad range of substrates, including ,-
unsaturated ketones, esters, amides, nitroalkenes, and
imines, could be arylated in high yields with excellent
enantioselectivities, and the catalyst could be reused
more than 10 times without any loss of either yield or
enantioselectivity.
Chiral diene ligands, pioneered by Hayashi[6] and
Carreira,[7] are well-studied class of ligands to
construct chiral transition metals such as Rh and Ir
catalysts, and they are utilized in many catalytic
asymmetric reactions, including asymmetric arylation
of electron-deficient olefins.[8-11] In our laboratory, we
have developed diene L with tertiary alkyl amine-
derived secondary amide, which was designed as a
bifunctional ligand where the diene parts could
coordinate to metal and the relatively acidic secondary
amide group could activate substrates through
hydrogen bonding (Scheme 1). The ligand was applied
1
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
Scheme 1. Tertiary alkyl amine-derived secondary amide
substituted diene.
ratios of styrene, DVB, and the chiral diene monomer
(entry 5).
Table 1. Optimization of reaction conditions.
Considering our previous investigations, the tertiary
alkyl amine moiety in diene L is essential to achieve
outstanding activity and enantioselectivity, probably
because structurally rigid nature of the amide group
that restricts the rotation of the tBuNH group to fix the
favored conformation.[13] In the above-mentioned
previous examples of immobilized dienes, the dienes
were conjugated to primary amines on supports by
amide condensation; however, they could not
introduce a tertiary alkyl amine moiety probably
because of difficulty to prepare a tertiary alkyl amine-
containing support. Therefore, we designed a tertiary
alkyl amine-derived chiral diene ligand with a styryl
moiety to immobilize the ligand directly by
polymerization. Such a strategy has never been
conducted, presumably because it is concerned that an
unsaturated carbonyl moiety in a ligand might induce
side reactions under radical polymerization conditions.
We synthesized a chiral diene monomer bearing a
styrene moiety (see the Supporting Information (SI)),
and as shown in Scheme 2, the diene monomer was
O
O
PS-diene Rh–Cl (Rh: 0.5 mol%)
tol/H2O = 1:2, 100 °C, 16 h
+
PhB(OH)2
1.5 equiv
Ph
1a
2a
3aa
ee (%)b)
entry catalyst x:y:z
yield (%)a)
1
2
3
4
5
96:2.5:1.3
95:3.6:1.3
93:6.0:1.3
96:3.6:0.7
94:3.6:2.6
75
86
74
91
98
99
99
99
99
99
A
B
C
D
E
a) Determined by 1H NMR analysis. b) Determined by
HPLC analysis.
With PS-diene Rh−Cl E (0.5 mol%), several
reactions of boronic acids with ,-unsaturated
carbonyl compounds were examined (Table 2).
Neither electron-withdrawing nor electron-donating
groups at the para-position of arylboronic acids (2b
and 2c) affected the catalytic activity, and high yields
and outstanding enantioselectivities of the desired
products were obtained (entries 2 and 3). meta-
Methoxyphenylboronic acid (2d) was also a suitable
substrate (entry 4). Arylboronic acid 2e, with a
substituent at the ortho-position, gave the desired
product in lower yield (69%), presumably because of
a steric effect, but outstanding enantioselectivity was
observed (entry 5). The yield was improved to 92% by
using 3 equiv. of 2e while keeping the same
enantioselectivity. As previously reported,[12] lower
reactivity was observed for acyclic ,-unsaturated
ketones than for cyclic ,-unsaturated ketone. For
example, acyclic ,-unsaturated ketone 1b reacted
with 2a to afford the product in only 5% yield,
although the enantioselectivity was very high (entry 6).
Other acyclic ,-unsaturated ketones 1c and 1d
showed moderate to good yields, albeit with very high
enantioselectivities (entries 7 and 8). These low-yield
issues were solved later (see below). When acyclic
,-unsaturated ester 1e was treated with 2a, the
desired product was obtained in 76% yield with 98%
ee. Given that decomposition of the boronic acid was
observed, 3.0 equiv. of 2a were used and the yield was
improved to 99% with the same enantioselectivity
(entry 9). Other ,-unsaturated esters, including
heteroaromatics and even cyclic ,-unsaturated
esters, also worked well to afford the desired products
carefully copolymerized
with
styrene
and
divinylbenzene (DVB) in the presence of AIBN (0.8
mol%) at 80 °C, affording a chiral diene ligand
supported on cross-linked polystyrene (PS-diene). PS-
diene was then mixed with [Rh(C2H4)2Cl]2 in toluene
to afford a yellow powder (PS-diene Rh−Cl).
Successful immobilization of Rh was confirmed by
ICP-OES measurements. STEM images and EDS
analysis showed that Rh was well dispersed on
polymer and the absence of Rh nanoparticles (see SI).
Notably, PS-diene Rh−Cl was readily prepared, was
stable in air, and could be stored for several months.
Scheme 2 Immobilization of diene ligand.
in
satisfactory
yields
with
very
high
enantioselectivities (entries 10–15). Finally, ,-
unsaturated amides were tested, and it was found that
this type of compounds were acceptable to this
catalytic system (entries 16 and 17).
Recovery and reuse experiments of heterogeneous
PS-diene Rh−Cl E were conducted for the reaction of
2a with 1a (Table 3). Even after the 10th cycle, no loss
of either yield or enantioselectivity was observed. We
also compared the activity of PS-diene Rh E with the
PS-diene Rh−Cl A–E, with different ratios of
styrene, DVB, and the diene monomer, were tested in
the asymmetric 1,4-addition of phenylboronic acid
(2a) to cyclic enone 1a in toluene/water biphasic co-
solvent system[23] (Table 1). The highest yield with
outstanding enantioselectivity for the product 3aa was
obtained using PS-diene Rh−Cl E with 94:3.6:2.4
2
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
corresponding homogeneous Rh-diene L complex in
the reaction of 1e with 2a.[24] Although a similar high
yield was observed in the presence of 0.1 mol% of the
homogeneous catalyst, enough fast reaction rate and
reusability of the heterogeneous catalyst are still
remarkable advantages.
which are valuable because the resulting chiral nitro
compounds can be converted into a range of useful
compounds such as chiral amines. However, because
of the strong coordination ability of the nitro group,
stoichiometric to substoichiometric amounts of
additives, such as KOH or KHF2, were required to
achieve an efficient catalytic turnover.[25,26] Moreover,
reported examples of heterogeneous catalysts for this
asymmetric reaction have been very limited. We
conducted several reactions of boronic acids with
nitroalkenes using PS-diene Rh−Cl E (Table 4).
Nitrostyrene derivatives bearing either electron-
donating or electron-withdrawing substituents on the
benzene ring worked well (entries 1–5). Heteroarenes-
substituted nitroalkenes could react with 2a to afford
the corresponding adducts in high yields with high
enantioselectivities (entries 6 and 7). Even aliphatic
substrates could be utilized keeping high level of
enantioselectivity (entries 8 and 9). Notably, PS-diene
Rh-Cl E gave the same level or slightly higher
enantioselectivities compared with the corresponding
homogeneous Rh-diene L complex system.[16]
Table 2. Substrate scope (α,β-unsaturated carbonyl
compounds).
PS-diene Rh–Cl E (Rh: 0.5 mol%)
Ar
O
O
ArB(OH)2 2 (1.5 equiv)
R
X
R
X
tol/H2O = 1:2, 100 °C, 16 h
3aa-ma
1a-m
O
O
O
O
OEt
C5H11
1c
1b
1d
1e
O
O
O
O
OEt
O
OEt
OMe
1g
MeO
1h
1i
1f
O
O
O
O
N
Ph
OEt
OEt
N
H
Ph
H
S
1l
O
1k
1m
1j
We also examined asymmetric addition reactions of
arylboronic acids with imines using PS-diene Rh−Cl.
Since the first report of asymmetric addition of
arylboronic acids to aryl tosylimines catalyzed by
chiral Rh complexes in 2004,[27] many efforts have
been made to develop this type of reaction to provide
chiral amines, which are found in many
pharmaceutical skeletons.[28] By using PS-diene
Rh−Cl E (0.5 mol%), several imines were treated with
2a under the optimal conditions (Table 5). Regardless
of the substituents, all aromatic (entries 1–5) and
heteroaromatic imines (entries 6 and 7) worked well to
afford the corresponding amines in high yields with
outstanding enantioselectivities. Although aliphatic
imines are usually unstable in aqueous media, imine
6h could be smoothly converted to the corresponding
amine 7ha even in a water-rich co-solvent system
(entry 8). These results indicated that the immobilized
catalyst maintained enough fast reaction rate to avoid
hydrolysis of substrates.
B(OH)2
B(OH)2
MeO
B(OH)2
B(OH)2
MeO
F
2c
2b
2d
2e
entry 1
2
yield ee
entry 1
2
yield ee
(%)a) (%)b)
(%)a) (%)b)
1
98
88
90
94
99
99
99
99
99
9c)
99
89
80
93
76
98
98
98
98
98
1a 2a
1a 2b
1a 2c
1a 2d
1a 2e
1e 2a
1f 2d
1g 2d
1h 2a
1i 2a
2
3
4
5
10c)
11c)
12c)
13c)
69
(92)c)
5
6
7
8
99
99
96
14c)
15c)
16
60
95
89
96
96
95
98
98
1b 2a
1c 2a
1d 2d
1j 2a
1k 2a
1l 2a
1m 2a
(87)c,d)
25
(89)c,d)
64
(90)e)
17
a)
b)
c)
Isolated yield.
Determined by HPLC analysis.
ArB(OH)2 (3.0 equiv) was used. Cinnamyl alcohol (1.0
mol%) was used as an additive. PS-diene Rh−OH was
d)
Based on these studies of substrate scope, it was
revealed that chiral environments around the
immobilized Rh complex were not disturbed by the
e)
used.
polymer
matrix,
and
with
thus
the
comparable
corresponding
enantioselectivities
Table 3. Recovery and reuse.
homogeneous Rh-diene L catalyst could be achieved
for all the substrates regardless of electronically or
sterically affective substituents. The same absolute
configurations with the homogeneous catalyst were
observed, indicating that the mechanism of
enantioselection[16,29] might not be different. Such a
broad generality had never been achieved in
previously-reported immobilized Rh complex
catalysts.[24]
Ph
O
O
PS-diene Rh–Cl E (Rh: 1.0 mol%)
PhB(OH)2 2a (3.0 equiv)
OEt
OEt
tol/H2O = 1:2, 100 °C, 1 h
1e
3ea
cycle yield (%)a) ee (%)b) cycle yield (%)a) ee (%)b)
1
2
3
4
5
99
98
99
98
97
99
99
99
99
99
6
7
8
9
97
98
99
98
98
99
99
99
99
99
10
Table 4. Substrate scope (nitroalkenes).
a) Isolated yield. b) Determined by HPLC analysis.
We then investigated asymmetric 1,4-addition
reactions of aryl boronic acids with nitroalkenes,
3
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
95% for 30 min; 96% for 1 h (99% ee)). We also
conducted the reactions of acyclic ,-unsaturated
ketones 1b, 1c, and 1d, and it was found that the yields
were improved significantly (36%, 50%, 90%,
respectively, Table 2, entry 8 in parentheses).
Although the yields were improved, PS-diene Rh−OH
was hygroscopic and its handling was not easy. We
then intended to prepare PS-diene Rh−OH in situ from
PS-diene Rh−Cl. After screening several additives
(see SI), it was found that the use of and cinnamyl
alcohol (1.0 mol%), 1b and 1c reacted with 2a to
afford cinnamyl alcohol was very effective for the
reactions. In the presence of PS-diene Rh−Cl (0.5
mol%) and cinnamyl alcohol (1.0 mol%), 1b and 1c
reacted with 2a to afford the corresponding adducts
3ba and 3ca in 55% and 65% yields, respectively. The
yields were further improved to 87% and 89%,
respectively, by using 3 equiv. of 2a while maintaining
outstanding enantioselectivity (Table 2, entries 6 and
7 in parentheses). We assume that cinnamyl alcohol
coordinates to Rh of PS-diene Rh−Cl to accelerate the
formation of PS-diene Rh−OH. In this heterogeneous
Rh-catalyzed asymmetric arylation of ,-unsaturated
carbonyl compounds without using additives, the
efficiency of the reaction of esters and amides was
better than that of ketones, despite the lower
electrophilicity of unsaturated esters and amides. We
assume that more Lewis basic esters and amides may
also work as additives, coordinating to Rh of PS-diene
Rh-Cl to accelerate the formation of PS-diene
Rh−OH.[32,33]
PS-diene Rh–Cl E (Rh: 0.5 mol%)
Ar
ArB(OH)2 2 (1.5 equiv)
NO2
NO2
R
R
tol/H2O = 1:2, 100 °C, 16 h
5ad-ia
4a-i
NO2
NO2
NO2
NO2
NO2
4a
MeO
NO2
4c
Me
Br
4b
NO2
NO2
O
F
4d
4g
4e
4f
4i
NO2
4h
S
entry 4
2
yield ee
entry 4
2
yield ee
(%)a) (%)b)
(%)a) (%)b)
1
2
3
4
5
88
91
95
92
94
94
93
95
93
93
6
7
8
9
93
93
90
94
96
93
90
89
4a 2d
4b 2a
4c 2a
4d 2a
4e 2a
4f 2a
4g 2a
4h 2a
4i 2a
a) Isolated yield. b) Determined by HPLC analysis.
Table 5. Substrate scope (imines).
PS-diene Rh–Cl E (Rh: 0.5 mol%)
Ph
PhB(OH)2 2a (1.5 equiv)
Ts
Ts
R
N
H
R
N
tol/H2O = 1:2, 100 °C, 16 h
6a-h
7aa-ha
Ts
Ts
Ts
N
Ts
N
N
N
Cl
MeO
The application of PS-diene Rh−OH to a
continuous-flow reaction was conducted (Scheme 3).
A toluene solution of 1a and an aqueous solution of 2a
were mixed in a T-shape joint and the biphasic flow
was passed through the column containing PS-diene
Rh−OH with back pressure. The desired product was
continuously obtained in high yield without any
decrease in enantioselectivity from batch reaction.
However, clogging occurred after several hours.
Further improvements to the catalysts are therefore
required to enable continuous flow to be operated with
a long lifetime; such a project is ongoing in our
laboratory.
6c
6a
6b
6d
Ts
Ts
Ts
Ts
N
N
N
N
S
O
Br
6g
6e
6h
6f
entry
6
yield
(%)a)
ee (%)b)entry
6
yield
(%)a)
ee (%)b)
1
2
95
93
98
98
99
98
99
98
5c)
6
89
85
90
78
97
99
99
99
6a
6b
6c
6d
6e
6f
6g
3
7
4c)
8c)
6h
a) Isolated yield. b) Determined by HPLC analysis.
While various substrates in asymmetric 1,4-addition
and even 1,2-addition reactions proceeded well, the
lower yield associated with acyclic ,-unsaturated
ketones remained. It is known that the active species
in Rh-catalyzed 1,4-addition reactions are Rh−OH
complexes,[30] and that treatment of Rh−Cl complexes
with
a
base generates more active Rh−OH
complexes.[31] We then treated PS-diene Rh−Cl with
KOH at room temperature for 24 h to form a
hygroscopic solid, the elemental analysis of which
showed a significant decrease in the amount of Cl,
suggesting Rh−OH formation (see SI). The solid PS-
diene Rh−OH thus prepared was first tested in the
asymmetric 1,4-addition reaction of 2a with 1a. The
reaction proceeded very rapidly to afford the desired
adduct 3aa quantitatively within 30 min; the TOF of
the catalyst reached over 1,000 h–1 (91% for 10 min;
Scheme 2. Continuous-flow reaction.
In conclusion, we have developed ligand-
immobilized heterogeneous chiral Rh complexes (PS-
diene Rh−Cl) for asymmetric arylation reactions. A
broad range of substrates, including ,-unsaturated
4
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
ketones, ,-unsaturated esters, ,-unsaturated
amides, nitroalkenes, and imines, could be arylated in
high yields with excellent enantioselectivities, and the
catalyst could be reused more than 10 times without
any loss of yield or enantioselectivity. PS-diene Rh−Cl
is robust and superior to previous-reported
heterogeneous catalysts for the same type of
reactions[17-22] and has comparable performance with
the corresponding homogeneous catalyst.[13,16] These
results indicated that the chiral diene with the tertiary
alkyl amine-derived secondary amide moiety was
successfully immobilized even under radical
polymerization conditions. PS-diene Rh−Cl was
further activated either by treatment with a base or in
the presence of a Lewis basic additive. High TOF
(>1000 h–1) was achieved and the activated catalyst
was applied to an asymmetric continuous-flow
reaction.
[7] C. Fischer, C. Defieber, T. Suzuki, E. M. Carreira, J. Am.
Chem. Soc. 2004, 126, 1628–1629.
[8] K. Okamoto, T. Hayashi, V. H. Rawal, Chem. Commun.
2009, 4815–4817.
[9] C. Defieber, H. Grützmacher, E. M. Carreira, Angew.
Chem. Int. Ed. 2008, 47, 4482–4502.
[10] R. Shintani, T. Hayashi, Aldrichimica Acta 2009, 42,
31–38.
[11] C. G. Feng, M. H. Xu, G. Q. Lin, Synlett 2011, 1345–
1356.
[12] T. Yasukawa, H. Miyamura, S. Kobayashi, J. Am.
Chem. Soc. 2012, 134, 16963–16966.
[13] T. Yasukawa, A. Suzuki, H. Miyamura, K. Nishino, S.
Kobayashi, J. Am. Chem. Soc. 2015, 137, 6616–6623.
[14] T. Yasukawa, Y. Saito, H. Miyamura, S. Kobayashi,
Angew. Chem. Int. Ed. 2016, 55, 8058–8061.
Experimental Section
[15] T. Yasukawa, T. Kuremoto, H. Miyamura, S.
Kobayashi, Org. Lett. 2016, 18, 2716–2718.
Representative procedure of asymmetric arylation
catalyzed by PS-diene Rh catalyst.
[16] H. Miyamura, K. Nishino, T. Yasukawa, S. Kobayashi,
Chem. Sci. 2017, 8362–8372.
PS-diene Rh (0.189 mmol/g, 7.9 mg, 0.0015 mmol,
phenylboronic acid 2a (53.7 mg, 0.45 mmol) and 2-
cyclohexenone 1a (28.8 mg, 0.3 mmol) were mixed with
toluene (700 L) and water (1400 L). After the mixture
was stirred at 100 °C for 16 h, the resulting mixture was
diluted with Et2O, washed with saturated aqueous Na2CO3
twice and dried over Na2SO4, and the solvent was removed
[17] Y. Otomaru, T. Senda, T. Hayashi, Org. Lett. 2004, 6,
3357–3359.
[18] R. Jana, J. A. Tunge, Org. Lett. 2009, 11, 971–974.
[19] R. Jana, J. A. Tunge, J. Org. Chem. 2011, 76, 8376–
1
in vacuo. The conversion was determined by H NMR
8385.
analysis with reference to an internal standard (1,1,2,2-
tetrachloroethane). The crude product was purified by pTLC
(hexane/ethyl acetate = 10:1) to afford the pure product 3aa
(51.2 mg, 98% yield). The ee value of the product was
determined by chiral HPLC analysis (99% ee).
[20] B. H. Lipshutz, N. A. Isley, R. Moser, S. Ghorai, H.
Leuser, B. R. Taft, Adv. Synth. Catal. 2012, 354, 3175–
3179.
[21] T. Sawano, P. Ji, A. R. McIsaac, Z. Lin, C. W. Abney,
W. Lin, Chem. Sci. 2015, 6, 7163–7168.
Acknowledgements
[22] G. Shen, T. Osako, M. Nagaosa, Y. Uozumi, J. Org.
Chem. 2018, 83, 7380–7387.
This work was partially supported by a Grant-in-Aid for Science
Research from the Japan Society for the Promotion of Science
(JSPS) and the Ministry of Education, Culture, Sports, Science and
Technology (MEXT) and the Japan Science and Technology
Agency (JST). T. K. acknowledges the MERIT program, The
University of Tokyo.
[23] Monophasic system was not suitable for this reaction.
See SI for detail.
[24] See SI for detail.
[25] Z. Q. Wang, C. G. Feng, S. S. Zhang, M. H. Xu, G. Q.
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
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10.1002/adsc.201900526
Advanced Synthesis & Catalysis
COMMUNICATION
Heterogeneous Chiral Diene-Rh Complexes for
Asymmetric Arylation of α,β-Unsaturated
Carbonyl Compounds, Nitroalkenes, and Imines
Adv. Synth. Catal. Year, Volume, Page – Page
broad substrates
(ketones, esters,
amides, imines,
nitroalkenes)
Tatsuya Kuremoto, Tomohiro Yasukawa and Shū
Kobayashi*
up to 99% yield
up to 99% ee
PS-diene Rh–Cl
7
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