Chiral Phosphorus-Olefin Ligands for the RhI-Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins

Article abstract of DOI:10.1002/asia.201600143

New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; t

Full text of DOI:10.1002/asia.201600143

DOI: 10.1002/asia.201600143
Communication
Asymmetric Arylation
Chiral Phosphorus–Olefin Ligands for the RhI-Catalyzed
Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient
Olefins
Qian Chen,*[a] Liang Li,[a] Guangli Zhou,[b] Xiaoli Ma,[a] Lu Zhang,[a] Fang Guo,[a] Yi Luo,*[b] and
Wujiong Xia*[a]
prepared.[5,6] As a coordination group, olefins are really fasci-
Abstract: New chiral phosphorus–olefin hybrid ligands de-
rived from the rigid “privileged” l-proline have been con-
veniently prepared and applied in the rhodium-catalyzed
asymmetric arylation of electron-deficient olefins with aryl-
boronic acids at room temperature; this reaction provides
the desired products in excellent yields and high enantio-
selectivities. The origin of observed stereoselectivity has
been investigated by density functional theory (DFT) cal-
culations.
nating due to its enormous potency, which can be installed
into many “privileged” skeletons and/or combined with the
other existing coordination atoms and/or functional groups. In
fact, the recently developed olefin-containing chiral ligands,
alkene, P-,[7] alkene, N-[8] and alkene, S-hybrid[9,10] ligands have
shown novel coordination ability and higher catalytic per-
formance in asymmetric catalysis, and attracted considerable
attention from several research groups.
We have also engaged in this interesting research field and
described that chiral N-tert-butylsulfinyl vinyl aziridines and C2-
symmetric chiral sulfurous diamides can be used as efficient
chiral sulfur–olefin hybrid ligands for highly enantioselective
rhodium-catalyzed asymmetric 1, 4-addition reactions.[11] In this
context, considering the outstanding coordination ability of
phosphorus, the exploitation of new ligands based on the
olefin, P-hybrid compounds would unambiguously enrich the
chiral ligand libraries and enhance their application in asym-
metric organic synthesis. Herein, we describe the development
of a new class of olefin, P-ligands based on the rigid “privi-
leged” chiral pyrrolidine backbone.
Chiral molecules are important in the field of pharmaceuticals,
agricultural chemicals, fine chemicals, and materials. Catalytic
asymmetric synthesis of enantiomer-enriched compounds in
the presence of a catalytic amount of metal complexes modi-
fied with various chiral ligands has been proven to be one of
the most efficient approaches.[1] It will be a lasting topic of
great interest in asymmetric catalysis for the design and appli-
cation of novel chiral ligands, because a versatile chiral ligand
has never been reported. In this regard, the exploitation of
phosphorus- and nitrogen-based chiral ligands has given us
a distinct impression.[2]
We originally conceived that chiral phosphorus–olefin li-
gands would be obtained by combining a simple chiral phos-
phinamine with cinnamyl group. Therefore, we started our re-
search by preparing chiral phosphorus–olefin compounds 1a
and 1b and their application as ligands in the rhodium-cata-
lyzed asymmetric 1,4-addition of phenyl boronic acid to cyclo-
hexenone (Scheme 1). The chiral phosphorus–olefin com-
pounds 1a and 1b can be directly obtained by a simple two-
step procedure. Reductive amination of (S)-1-phenylethana-
mine or (S)-1-cyclohexylethanamine with cinnamaldehyde gave
the corresponding secondary amine in high yield. N-phosphi-
On the one hand, the discovery of organometallic com-
plexes with olefin ligand(s) in organometallic chemistry has
a long and continuing history.[3] However, the use of catalytic
organometallic complexes with chiral olefin ligand(s) was only
achieved recently by the research groups of Hayashi and Car-
reira; this encouraged a dramatic surge of research interest in
asymmetric catalysis.[4] Subsequently, various diene ligands
with bicyclic and acyclic skeletons have been designed and
[a] Prof. Dr. Q. Chen, L. Li, X. Ma, L. Zhang, F. Guo, Prof. Dr. W. Xia
State Key Lab of Urban Water Resource and Environment (SKLUWRE)
School of Chemistry and Chemical Engineering
Harbin Institute of Technology
Harbin, Heilongjiang, 150080 (China)
E-mail: chenqian@hit.edu.cn
[b] G. Zhou, Prof. Dr. Y. Luo
State Key Laboratory of Fine Chemicals
School of Pharmaceutical Science and Technology
Dalian University of Technology
Dalian 116024 (China)
Supporting information for this article can be found under http://
dx.doi.org/10.1002/asia.201600143.
Scheme 1. Initial attempts using chiral olefins, P-ligands for the RhI-catalyzed
asymmetric arylation.
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nation of the secondary amines with chlorodiphenyl phos-
phine completed the synthesis of 1 in good yield. When 1a
and 1b were used as a chiral ligand for the rhodium-catalyzed
asymmetric 1,4-addition reaction, the adduct was obtained in
good-to-high yield with promising enantioselectivity (30% ee).
Based on the above encouraging results, we designed
a kind of novel chiral phosphorus–olefin ligand bearing a “privi-
leged” chiral pyrrolidine backbone (Figure 1). We further envi-
Table 1. Effect of the chiral phosphorus–olefin ligands in the Rh-cata-
lyzed asymmetric addition of phenylboronic acid to cyclohexenone.
Entry[a]
Ligand
T [8C]
t [h]
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
1c
1c
1d
1e
1 f
1g
70
25
25
25
25
25
3
99
98
98
99
89
97
85
90
90
89
81
93
10
10
12
12
12
Figure 1. Design of new chiral phosphorus–olefin hybrid ligand.
[a] All reactions were carried out with 4a (0.5 mmol) and 5a (2.5 mmol)
in 1,4-dioxane (2.0 mL) unless otherwise noted. [b] Isolated yield. [c] De-
termined by chiral HPLC with hexane/2-propanol.
sioned that the stereocontrol performance of the ligand in
asymmetric catalysis can be improved by introducing a rigid
five-membered cyclic backbone, which can be readily obtained
from l-proline, and the chiral carbon of the ligand is closer to
the alkenyl group compared to that of 1a and 1b. Further-
more, the modularity of aryl group would make it possible to
discover ideal ligands. It should be noted that most of the re-
ported chiral phosphorus–olefin ligands are prepared by chiral
resolution or tedious synthetic procedures, and few are de-
rived from natural chiral pool compounds.[7k] This is the first
successful example of a designed chiral phosphorus–olefin
hybrid ligand governed by natural amino acid, l-proline.
The synthesis of ligands 1c–1g is shown in Scheme 2; this
started from the commercially available (S)-(À)-1-Boc-2-pyrroli-
dinemethanol in several sample steps (Boc=tert-butoxycar-
bonyl).[12] Oxidation of the alcohol gave the corresponding al-
dehyde 2 in 83% yield using copper-catalyzed air oxidation.[13]
3 mol% Rh-1c complex at 708C (Table 1, entry 1). When the re-
action temperature was reduced to room temperature (258C),
the enantioselectivity increased to 90% ee (Table 1, entry 2).
Then, electronic and steric effects of the aryl group in the
chiral phosphorus–olefin ligands were examined (Table 1, en-
tries 3–6). The electronic effect of aryl group in chiral phospho-
rus–olefin ligands has no distinct influence on catalytic activity,
whereas the position of the substituent on the phenyl ring has
a little influence on the enantioselectivity. For example, both li-
gands 1d bearing electron-withdrawing substituted groups
and 1e bearing electron-donating substituted groups gave the
products in excellent yield with 90% ee and 89% ee, respec-
tively (Table 1, entries 3 and 4). However, the attempt to im-
prove the enantioselectivity, by introducing two methyl groups
at the ortho-position of benzene, has proven to be challenging,
as a lower enantioselectivity (81% ee) despite maintaining
higher yield (Table 1, entry 5) was obtained. The enantioselec-
tivity of this catalytic reaction improved to 93% ee when
ligand 1g was used, in which the methyl substituent of 3,5-di-
methoxyl benzene in ligand 1e was replaced by benzyl
(Table 1, entry 4 vs entry 6).
With the optimal reaction conditions in hand (Table 1,
entry 6), the scope of this rhodium-catalyzed asymmetric 1,4-
addition reaction was then investigated. As shown in Table 2,
the substituents of substrate 5 may be either electron-rich or
electron-deficient aryl groups, which had very little effect on
the reaction stereoselectivity. For example, 3-methoxyphenyl
and 4-methoxyphenyl, the aryl groups of which have electron-
donating groups were successfully introduced to 4a, thereby
giving the corresponding product 6 with high enantioselectivi-
ty in excellent yields (Table 2, entries 2 and 3, 90% ee). 4-Chlor-
ophenyl bearing an electron-withdrawing substituent was also
introduced to 4a to give 6ad in good yield and excellent ee
(93%) (Table 2, entry 4). The reaction of 2-methylphenyl, 2-
naphthyl, 3,5-dimethylphenyl, and 4-methylphenyl boronic
acid with 4a gave the corresponding product 6 in excellent
yield (90–98%) with good enantioselectivity (84–88% ee)
(Table 2, entries 5–8). Then, cyclopentenone 4b was examined
as a substrate for this transformation. Thus, the reactions of cy-
Scheme 2. Synthesis of chiral olefins, P-ligands derived from the l-proline.
A Horner–Wadsworth–Emmons olefination reaction of the al-
dehyde 2 with phosphonate afforded alkene 3 in good-to-high
yields. Removal of the Boc group and subsequent N-phosphi-
nation with chlorodiphenyl phosphine completed the synthesis
of 1 in moderate-to-high yields over two steps.
With chiral phosphorus–olefin ligands 1c–1g in hand, the
RhI-catalyzed 1,4-addition of phenylboronic acid 5a with cyclo-
hexenone 4a was reexamined as the model reaction to evalu-
ate its efficiency in asymmetric catalysis.[14] As expected, the
product 6aa was formed in excellent yield (>99%) and rea-
sonably high enantioselectivity (85% ee) in the presence of
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Table 2. Rh/1g-catalyzed asymmetric addition of arylboronic acids 5 to
a,b-unsaturated carbonyl compounds 4.
Scheme 3. Asymmetric addition of arylboronic acid 5c to nitroalkene 7.
Entry[a]
4
ArB(OH)2
t [h]
6
Yield [%][b]
ee [%][c]
Figure 2. Proposed stereochemical model.
1
2
3
4
5
6
7
8
4a
4a
4a
4a
4a
4a
4a
4a
4b
4b
4b
4b
4b
4c
4d
5a
5b
5c
5d
5e
5 f
5g
5h
5a
5c
5e
5 f
5g
5c
5c
10
8
8
6aa
6ab
6ac
6ad
6ae
6af
6ag
6ah
6ba
6bc
6be
6bf
6bg
6cc
6dc
97
93
99
70
98
95
90
90
95
99
96
95
98
73
95
93
90
90
93
87
88
88
84
86
91
93
84
90
87
92
group of ligand and carbonyl or methyene of 6-position in cy-
clohexenone 4a. Accordingly, the phenyl group in the metal
center attacks the activated olefin from the a si-face to give
the corresponding adduct (S)-6aa, which is in agreement with
the observed result. The absolute configuration of 6aa was de-
termined to be S by comparing its optical rotation value with
the literature.[15]
8
10
12
8
12
10
12
12
12
10
10
12
9
10
11
12
13
14
15
To see the transition structures related to the stereochemis-
try, DFT calculations were conducted (see the Supporting Infor-
mation for computational details). As shown in Figure 3, cyclo-
hexenone (B) would adopt the si-face to coordinate with phe-
nylrhodium species (A) to give coordination complex (C),
which is exergonic by 2.9 kcalmolÀ1. Then C overcomes an
energy barrier of 14.9 kcalmolÀ1 to give species E with (S)-con-
figuration. However, the re-face insertion process has a higher
energy barrier (17.8 kcalmolÀ1), endergonic coordination com-
plex (D, 2.1 kcalmolÀ1) and thermodynamically less favorable
addition product F. This result is in line with the observed ste-
reochemical outcomes. It is noteworthy that all of the opti-
mized structures show a strong interaction between the Rh
and HC=CHPh double bond of the ligand, as suggested by the
RhÀC distances of 2.19 Š–2.45 Š (see Figure S1 in the Support-
ing Information).
[a] All reactions were carried out with 4a (0.5 mmol) and 5a (2.5 mmol)
in 1,4-dioxane (2.0 mL) unless otherwise noted. [b] Isolated yield. [c] De-
termined by chiral HPLC with hexane/2-propanol.
clopentenone 4b with several arylboronic acids, the aryl
groups of which have electron-donating and electron-with-
drawing substituted groups, took place smoothly to afford the
corresponding 6 with good-to-high enantioselectivity (84–93%
ee) in excellent yields (Table 2, entries 9–13). Furthermore,
linear a,b-unsaturated carbonyl compounds were also good
substrates for this transformation. The reaction of enone (E)-4-
phenylbut-3-en-2-one 4c with 4-methoxyphenyl boronic acid
5c afforded 6cc in good yield and high enantioselectivity
(87% ee) (Table 2, entry 14). The reaction of methyl cinnamate
4d with 4-methoxyphenyl boronic acid 5c gave the product
6dc in 95% yield with 92% ee (Table 2, entry 15).
Finally, we further examined the substrate scope other than
a,b-unsaturated carbonyl compounds. Thus, the transforma-
tion of nitroalkene 7 to the synthetically useful intermediate 8
was carried out (Scheme 3). The enantioselective addition of 4-
methoxyphenyl boronic acid 5c to 7 in the presence of a rhodi-
um/1g catalyst afforded product 8 in 79% yield with 70% ee.
The stereochemical pathway in our arylation of cyclohexe-
none 4a with 1g as the ligand is rationalized in Figure 2.[7c,f,h]
After the initial transmetalation step, the phenylrhodium spe-
cies has a trans-relationship between the phenyl group and
the olefin of ligand 1g. In the following step, cyclohexenone
4a preferentially approaches the vacant position of rhodium
with its a si-face to avoid the steric repulsion between the aryl
To further access the origin of the stereoselectivity, an
energy decomposition analysis was carried out.[16] The result in-
dicates that the catalyst moiety in the transition state TS (D–F)
with (R)-configuration is more deformed due to the repulsion
between the Ph group of the ligand and the carbonyl group
and neighboring methylene of cyclohexanone moiety in com-
parison with TS (C-E) with (S)-configuration.[16] This is similar
for the coordination complexes D and C. This could account
for the stabilities of C and TS (C–E), and why the (S)-configured
addition product E is more favorable.
In conclusion, we have successfully developed a new type of
chiral phosphorus–olefin hybrid ligands based on the rigid
“privileged” L-proline backbone, and demonstrated their utility
in enantioselective rhodium-catalyzed asymmetric arylation of
electron-deficient olefins with arylboronic acids at room tem-
perature. The adducts can be obtained in high yields and high
enantioselectivities. DFT calcualtions suggest that the repulsion
between the Ph group of ligand and the carbonyl and neigh-
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Figure 3. Computed energy profiles (energies in kcalmolÀ1) for the different stereochemical pathways in the arylation of cyclohexenone and the arylrhodium
species. Solid line denotes the si-face insertion to give the (S)-configuration, and the dashed line denotes the re-face insertion to give the (R)-configuration.
General procedure for rhodium(I)-catalyzed asymmetric 1,4-ad-
dition of phenylboronic acid to cycloalkenones: Under an atmos-
phere of N2, a reaction flask was charged with ([Rh(C2H4)2Cl]2
(2.9 mg, 0.0075 mmol) and PhB(OH)2 (2.5 mmol). Then, 1,4-dioxane
(2.0 mL), ligand (0.018 mmol), cyclohexenone (0.5 mmol), and 4m
aqueous potassium hydroxide (0.5 mmol) were added successively
to the flask. The mixture was stirred at room temperature. After di-
lution with AcOEt (20 mL), the mixture was washed with 10%
aqueous NaOH and brine, and then dried over Na2SO4, concentrat-
ed under vacuum, and purified by silica gel column chromatogra-
phy. The products were then analyzed by HPLC on a chiral station-
ary phase to determine the enantiomeric excess.
boring methylene of cyclohexanone accounts for the stereose-
lectivity. The simple synthesis and the modularity make this
new type of ligand attractive and promising for asymmetric
catalysis. Further modification of more effective chiral phos-
phorus–olefin hybrid ligands derived from l-proline and their
applications in other asymmetric transformations is currently
underway in our laboratory.
Experimental Section
General procedure for the synthesis of olefin from l-prolinal: To
a solution of diethyl benzylphosphonate (1.5 mmol) in THF (5 mL)
was added nBuLi (2.4m in hexane, 0.63 mL, 1.5 mmol) at À788C
over 5 min, and then the reaction mixture was stirred at the same
temperature for 1 h. A solution of l-prolinal (1 mmol) in THF was
added to the above solution. At this temperature, it was stirred for
1 h and then allowed to warm to room temperature. After being
stirred overnight, water (20 mL) was added to quench the reaction.
The aqueous phase was extracted by AcOEt (3”20 mL) and the
combined organic phases were washed with brine and dried over
anhydrous Na2SO4 and evaporated under vacuum. The desired
products were isolated by silica gel column chromatography.
Acknowledgements
We gratefully acknowledge financial support from SKLUWRE
(No.2014TS04), “the Fundamental Research Funds for the Cen-
tral Universities” (Grant No. HIT. IBRSEM.A.201404), and the Nat-
ural Science Foundation of China (NSFC Nos. 21429201 and
20902015).
Keywords: asymmetric arylation · electron-deficient olefins ·
ligands · L-proline · rhodium
General procedure for the synthesis of the chiral olefin, P-li-
gands: AcCl (10 mmol) was slowly added to an oven-dried 25 mL
flask charged with dried methanol (10 mL) at 08C. The resulting
mixture was stirred for 1 hour at room temperature. A solution of
olefin (1 mmol) in dried 1,4-dioxane (5 mL) was added to the reac-
tion mixture. The resulting mixture was stirred for 3 h at room tem-
perature. The solvent was removed and then an aqueous solution
of 10% NaOH (10 mL) was added. The reaction mixture was ex-
tracted with CH2Cl2 and the organic phases were dried over Na2SO4
and evaporated under vacuum to give a colorless oil. To this oil in
CH2Cl2 was added Et3N (5 mmol) and PPh2Cl (2 mmol) in CH2Cl2 at
08C. The mixture was stirred at room temperature for 6–10 h. The
residue was purified by silica gel chromatography to give the de-
sired ligand.
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Manuscript received: February 1, 2016
Revised: March 13, 2016
Accepted Article published: March 27, 2016
Final Article published: April 18, 2016
Chem. Asian J. 2016, 11, 1518 – 1522
www.chemasianj.org
1522
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim