Enantioselective hydrogenation of N-heteroaromatics catalyzed by chiral diphosphine modified binaphthyl palladium nanoparticles

Article abstract of DOI:10.1039/c7cy01672g

The first application of binaphthyl-stabilized palladium nanoparticles (Bin-PdNPs) with chiral modifiers in asymmetric hydrogenation of N-heteroaromatics is revealed. With an appropriate ratio of R-BINAP/Bin-PdNPs used, the pre-prepared chiral nanocatalyst achieves asymmetric hydrogenations of 2-substituted quinolines with good to excellent yields and moderate enantioselectivities, which showed superior catalytic properties to the R-BINAP/Pd complex. Moreover, this protocol is also applicable to 2-substituted indoles.

Full text of DOI:10.1039/c7cy01672g

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DOI: 10.1039/C7CY01672G
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Enantioselective Hydrogenation of N-heteroaromatics Catalyzed
by Chiral Diphosphines Modified Binaphthyl Palladium
Nanoparticles
Received 00th January 20xx,
Accepted 00th January 20xx
Yun-Tao Xia,a Jing Ma,a Xiao-Dong Wang,a Lei Yang,a and Lei Wua,b,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The first application of binaphthyl-stabilized palladium asymmetric hydrogenation of ketones with excellent
nanoparticles (BIN-PdNPs) with chiral modifiers in asymmetric enantioselectivities.7 However, compared to the blooming of
hydrogenation of N-heteroaromatics is revealed. With an asymmetric C-X, C-C formations,8 the AH achieved by metal
appropriate ratio of R-BINAP/Bin-PdNPs used, the pre-prepared nanoparticles are still underdeveloped, thus, it is highly
chiral nanocatalyst achieves asymmetric hydrogenations of 2- desirable to develop novel nanocatalysts and expand
substituted quinolines with good to excellent yields and moderate applications to enrich this chemistry.
enantioselectivities, which showed superior catalytic properties
The asymmetric hydrogenation of quinolines and indoles,
over that of R-BINAP/Pd complex. Moreover, this protocol is also representative families of N-heteroaromatics, provided a
applicable to 2-substituted indoles.
powerful tool for the synthesis of enantiopure tetrahydro-
quinolines and tetrahydroindoles, which were widely found in
natural-occurring or synthetic bioactive compounds.9 Leading
scientists, such as Zhou, Fan and Kuwano, have made great
achievements in this process with transition metal complexes
of Ru, Rh, Ir and Pd.10 Among which, in 2014, the first
palladium-catalyzed AH of quinoline derivatives was developed
by Zhou et al, with substrates bearing 3-phthalimido
substitution.10h To be noted, to the best of our knowledge,
palladium nanoparticles has never been applied in AH of
quinolines and indoles so far.11
Metal nanoparticles as active sites in organic transformations
have attracted extensive interest to academic and industrial
communities for several decades.1 Metal nanoparticles
possessing large surface-to-volume ratio, dominantly facilitate
higher catalytic efficiency compared to that of bulky metals or
metal complexes. Contrarily, the unpassivated active sites tend
to aggregate and precipitate during the catalytic cycle. In order
to prevent the aggregation and improve the reusability,
organic stabilizers or inorganic supports are usually utilized
based on either coordination effects or physical disjunction.1
In terms of organic stabilizers, organic molecules bearing
coordinating groups of O, N, P, or S atoms represent the
prevalent strategies.2 For pioneering contributions in
asymmetric catalysis, the Orito’s platinum catalytic systems
(cinchonidine modified platinum nanoparticles)3 and tartaric
acid-modified nickel nanoparticles4 were widely recognized as
two classical systems for asymmetric hydrogenation (AH) of
C=O bonds (Scheme 1a). Afterwards, varieties of metal
nanoparticles, chiral ligands and immobilization methods,
including polymers, magnetic Fe3O4, SiO2, and CNTs (carbon
nanotubes), were developed.5 Notably, AH with nanocatalysts
has long been limited to the two systems, albeit much efforts
have been devoted.6 Intriguingly, in 2014, an elegant study
was revealed by Xiao and co-workers, who reported the first
chiral N,P-macrocyclic ligands stabilized iron nanoparticles for
It has to mention that the aforementioned coordinative
ligands-stabilized nanocatalyst are widely accepted as “semi-
heterogeneous”,1f which is usually accompanied by
a
homogeneous catalytic process, deriving from metal leaching
from the nanoparticles surface. This phenomenon might be
acceptable to non-asymmetric reactions, but lethal to
asymmetric ones, since the homogeneous metal species would
disturb the catalytic process. Therefore, the design of
nanocatalyzed asymmetric reactions would be a challenging
issue to distinguish the heterogeneous process from
homogeneous, but attractive. As
a
breakthrough of
stabilization model, the first metal-carbon bond stabilized gold
and platinum nanoparticles was report by Mirhalaf in 2006,12
which exhibited higher bond energy than that of traditional
metal-nitrogen or metal-sulfur bonds, offering a clearly
heterogeneous catalysis mode. To date, varieties of organic
transformations have been achieved with metal-carbon bond
stabilized palladium nanoparticles (MCBS-PdNPs).13 Our group
has also advanced a serial of MCBS-PdNPs for hydrogenation
and dehydrogenation of N-heterocycles, 14 in which covalent
binaphthyl stabilization was found to be the most efficient
way.14a It has been exemplified that the strong covalent metal-
carbon bonds would be easier to keep heterogeneous during
the catalytic cycle, providing a distinct catalytic pattern from
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J. Name., 2017, 00, 1-3 | 1
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the ligands/polymers-stabilized nanocatalysts or metal pressure, and reaction temperature dramatically affect the
complexes. Interestingly, this type of metal nanoparticles has enantioselectivity of the hydrogenated DpOroI:d10u.c10t.3V9iTe/wCh7AoCrutiYcg0leh1O6nn7l2ionGet
never been investigated in asymmetric reactions. Herein, as distinct, reactions in aprotic solvents exhibited better enantio-
our continuing interest in nanocatalysis,14,15 we will disclose control. Most importantly, the reactions in water with less
the first application of binaphthyl-stabilized palladium ratio of (R)-BINAP gave the racemic product 2a (entries 1-2), to
nanoparticles (Bin-PdNPs) in AH of 2-substituted quinolines our delight, 6% e.e. was detected while enhancing the
and indoles (Scheme 1, b).
phosphine ligand loading (entry 3). We reasoned that, the
percentages of coordinated nanoparticles in Table 1 keep well
consistent with the preliminary results. With less ligand used,
the spare active sites would lead to the racemic product;14a on
the contrary, excess ligands competitively occupied the active
sites against the coordination of substrates with particle
surface, thus impairing the catalytic efficiency. Consequently,
the pre-prepared chiral nanocatalyst with a ratio of Pd/BINAP (1:1.2)
was utilized for further optimizations. With trifluoroacetic acid (TFA)
as an additive in dichloromethane, the ee value could be improved
to 70% (entry 9). It is worthy to mention that the probable
acidolysis of Bin-PdNPs/(R)-BINAP upon TFA into the Pd(TFA)2/(R)-
BINAP complex can be ruled out, since the homogeneous palladium
complex has been proven to be ineffective in asymmetric
hydrogenation of 2-methylquinoline.10h Other optimizations by
altering hydrogen pressure, amount of additive, reaction
temperature and phosphine ligands (L2-L9) were screened (in S.I.).
Bidentate chiral phosphines (L2-L6) rended either better yields or
enantioselectivties than mondentate phosphines, but worse than
the performance of L1 (entries 10-14), probably due to the match or
mismatch of ligand dihedral angle, 17 coordination sits and substrate.
Intriguingly, the reported (R)-BINAP-stabilized palladium
nanoparticles [(R)-BINAP-PdNPs]8a,8b gave 85% yield for this
transformation under the optimized conditions, but with only 8%
e.e. (entry 15). The Bin-PdNPs itself was used as comparison in
the absence of chiral phosphine, which delivered no difference
in reactivity (entry 16 vs 9). Moreover, chiral covalent
binaphthyl-stabilized PdNPs (prepared from the corresponding
R- and S- Bis-diazonium salts, respectively) presented identical
enantio-control with the racemic one (entries 17, 18).
Eventually, a homogeneous counterpart, Bis-diazonium salts/
Pd(TFA)2/L1, furnished only trace amount of the hydrogenated
product (entry 19), confirming the heterogeneous nature of
our catalyst. These results collectively pointed to a fact that the
covalent binaphthyl groups and chiral ligands play synergistic roles
on the reactivity and enantioselectivity.
Scheme 1 Representative Metal Nanoparticles for Asymmetric
Hydrogenation (a); and This Work (b).
The Bin-PdNPs, consisting of Pd(0) and Pd(II), was prepared
by in-situ reduction of palladium acetate and 1,1’-binaphthyl-
2,2’-bis(diazonium-tetrafluoroborate
(denoted
as
Bis-
diazonium salts) according to our reported "one-phase
reduction" procedures with a size distribution of 2.5±0.5
nm.14a The resulting nanocatalyst was then coordinated with
(R)-BINAP (L1) in acetone (the size distribution was not
changed after coordination, see details in the Supporting
Information) before being applied in the AH of 2-methyl-
quinoline. The coordination status of Bin-PdNPs and (R)-BINAP
were monitored by 31P-NMR spectroscopy. Table 1 described
the in-situ coordination labelings of phosphine ligands. Free
(R)-BINAP lied in -15.64 ppm, but changed to 28.64 ppm after
being decorated on the particles surface. According to the
integration ratios of free ligands and coordinated ones on 31P-
NMR spectra, the percentages of (R)-BINAP decorated PdNPs
could be calculated (see details in S.I.). With 1.2 equivalents
(R)-BINAP used, the chiral ligands occupied 34% of the
nanoparticles surface (Table 1, entry 3), which reflected an
average value of chirally modified sites over non-chiral ones on
PdNPs surface. Higher loading of phosphine ligand would
decrease the percentage accordingly, which might be ascribed
to the result of π-π repulsion.16
Table 2 The effects of solvents and ratios of Bin-PdNPs/(R)-
BINAP for asymmetric hydrogenation of 2-methylquinoline.a
Table 1 31P-NMR monitored coordination of (R)-BINAP with
Bin-PdNPs a
.
Catalyst/
Ligand (mol%)
2/0.5 (L1)
1/0.5 (L1)
1/1 (L1)
1/1 (L1)
1/1 (L1)
1/1 (L1)
1/2 (L1)
5/6 (L1)
5/6 (L1)
5/6 (L2)
5/6 (L3)
5/6 (L4)
Solvent/
Additive
H2O/-
H2O/-
H2O/-
H2 pressure
/temp (oC)
balloon/25
balloon/25
balloon/25
balloon/25
balloon/25
balloon/25
balloon/25
30 atm/60
30 atm/60
30 atm/60
30 atm/60
30 atm/60
30 atm/60
Yield
Entry
/ee(%)
>95/0
>95/0
>95/6
>95/5
>95/8
>95/12
56/0
>95/8
>95/70
55/-21
52/6
1
2
3
4
5
6
7
8
toluene/-
ether/-
L1/Bin-PdNPs
(molar ratio)
0.5:1
0.75:1
1.2:1
Integration
ratio
1:1
0.6:1
0.4:1
Percentage on
Bin-PdNPs
26%
28%
34%
Entry
CH2Cl2/-
CH2Cl2/-
CH2Cl2/-
CH2Cl2/TFA
CH2Cl2/TFA
CH2Cl2/TFA
CH2Cl2/TFA
CH2Cl2/TFA
1
2
3
4
9
1.5:1
0.2:1
25%
10
11
12
13
As shown in Table 2, preliminary results indicated that the
ratios of Bin-PdNPs/(R)-BINAP, solvents, additive, hydrogen
56/21
90/0
5/6 (L5)
2 | J. Name., 2017, 00, 1-3
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14
15c
16
17
18
5/6 (L6)
5
Bin-PdNPs
(R)-Bin-PdNPs/L1 CH2Cl2/TFA
(S)-Bin-PdNPs/L1 CH2Cl2/TFA
Bis-diazonium
CH2Cl2/TFA
CH2Cl2/TFA
CH2Cl2/TFA
30 atm/60
30 atm/60
30 atm/60
30 atm/60
30 atm/60
30 atm/60
88/0
85/8
>95/0
>95/70
>95/70
e.e. values ranged from 47-55%. Moreover, oVwieiwnAgrtictloe Ontlhinee
heterogeneous nature, only cis-products were detected for
DOI: 10.1039/C7CY01672G
2,3-substituted indoles (3d-3h). Although this protocol
exhibited worse enantiocontrol for 2-alkyl substitutions than
that of palladium complex, we delightfully found that, for
more challenging substrates with 2-aryl substitutions (3l-3n),
our system gave good to excellent yields with e.e. values above
CH2Cl2/TFA
19d
trace
salts/Pd(TFA)2/L1
a
2-methylquinoline (1a, 0.1 mmol), 3 mL solvent, Bin-PdNPs
/
30%, whereas only <5% yield of the hydrogenated product was
(R)-BINAP, 36 h; Yields and e.e. values were determined by detected in Pd(TFA)2/(R)-8H-BINAP system.10j Besides, the
b
1HNMR and HPLC equipped with a chiral OJ-H column, results for 2-aryl-substituted indoles were comparable to the
respectively; (R)-BINAP-PdNPs as catalyst; Bis-diazonium recent case of ruthenium-DPEN complexes.18
c
d
salts (6.7 mg, 1.8 mol%), 5 mol% Pd(TFA)2, 6 mol% (R)-BINAP.
Table 4 Substrate scope of indoles.a
Entry
R1
R2
R3
Yield/e.e.
(4, %)[b]
With the optimal conditions in hand, we then evaluated the
generality of this protocol for various 2-substituted quinolines.
For 2-methyl substituted ones, electron-rich and electron-
deficient substituents, such as methyl, methoxy, and fluoro at
6-positions, were well tolerated, affording the hydrogenated
products with good to excellent yields, along with moderate
e.e. values (Table 3, entries 2-5). It is noticed that, asymmetric
hydrogenation of methyl 2-methyl-quinoline-6-carboxylate
1
2
3
4
5
6
7
8
H
Me
Me
Me
Me
Me
Me
Me
Me
H (3a)
H (3b)
H (3c)
Me (3d)
4-F-benzyl (3e)
4-MeO-benzyl (3f)
4-Me-benzyl (3g)
benzyl (3h)
85/64(R)
81/50(R)
92/47(R)
95/51(R)[c]
83/48(R) [c]
86/54(R) [c]
92/55(R) [c]
90/53(R) [c]
81/55(R)
86/53(R)
93/54(R)
76/31(S)
93/32(S)
51/35(S)
86/22(S)
5-F
5-Me
H
H
H
H
H
H
H
H
H
H
H
(
1e) furnished 2e with higher yield and enantioselectivity than
that of palladium complex (entry 5, e.e.: 59% vs 27%).10h In
particular, substrates with 2-ethyl and 2-aryl substituents were
viable to the nanocatalytic system with good yields, along with
moderate e.e. values ranged from 52-66%. To our delight,
these are the best results in palladium-based catalytic protocol
for asymmetric hydrogenation of 2-arylsubstituted quinolines,
which has not been achieved for palladium complex yet.
9
4-Me-benzyl H (3i)
3-Me-benzyl H (3j)
benzyl
Phenyl
p-tol
10
11
12
13
14
15
H (3k)
H (3l)
H (3m)
H (3n)
Table 3 Substrate scope of quinolines.a
p-F-C6H4
p-MeO-C6H4 H (3o)
H
[a] indole (3, 0.25 mmol), 3 mL DCM/TFA(1:1), Bin-PdNPs/(R)-8H-
[b]
Entry
R1
R2
Yield/e.e. (2, %)[b]
93/70(R)
95/62(R)
95/46(R)
71/54(R)
63/59(R)
86/66(R)
91/56(S)
BINAP (2 mol%/2.4 mol%), 1 equiv L-CSA, 50 atm H2, 24 h.
Isolated yield, e.e. values were determined on HPLC.
[c]
Cis-
1
2
3
4
5
6
7
8
9
10
H
Me (1a)
Me (1b)
Me (1c)
Me (1d)
configuration.
6-Me
6-MeO
6-F
Based on our experimental results and previous reports,14a,19
a
catalytic mechanism is proposed in Fig. 1. The protonated quinoline
(1a) docks on the Bin-PdNPs surface by π-π stacking with covalent
binaphthyl group and the coordination of nitrogen with palladium(0)
atoms. Subsequently, asymmetric hydrogenation occurs on C=N
bond at the proximal zero-palladium site modified with chiral
phosphine. This dual interaction mode clarifies the worse chiral
induction for individual (R)-BINAP-PdNPs8a,8b and the identical
results catalyzed by (R)-/(S)-Bin-PdNPs (Table 1, entries 17, 18).
Considering the percentage of chiral ligands modified surface (34%),
a competing mode of flat absorption of the quinoline moiety onto
the metal surface leads to the racemic product, which can explain
the moderate enantioselectivities obtained in this protocol.
6-COOMe Me (1e)
H
H
H
H
H
Et (1f)
Phenyl (1g)
o-tolyl (1h)
2,4-dimethylphenyl (1i)
84/46(S)
82/52(S)
76/53(S)
2-Naphthyl (1j)
a Isolated yield; e.e. values were determined on HPLC.
Our protocol can also be applied to the asymmetric
hydrogenation of indole derivatives. Nevertheless, the optimal
conditions developed for quinolines were not applicable
herein. Systematical conditions screening revealed that, with 2
mol% BIN-PdNPs/2.4 mol% (R)-8H-BINAP as catalyst, dichloro-
methane/trifluoroethanol (1:1) as solvent, L-CSA as additive,
and 50 atm H2, 2-methylindole underwent hydrogenation
smoothly (see more details in the S.I.). As depicted in Table 4,
2 or 2,3-substituted indoles proceeded with good to excellent
yields of hydrogenated products (4a-4k), albeit with moderate Fig. 1 Proposed Catalytic Mechanism.
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Chem. Soc. 2003, 125, 15742; b) K. Sawai, R. Tatumi, T.
Nakahodo, H. Fujihara, Angew. Chem. DInOtI.:E10d..1023090/C8,7C4Y701672G
View Articl,e 6O9nl1in7e;
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In summary, we revealed here the first application of
binaphthyl-stabilized palladium nanoparticles (Bin-PdNPs) with
chiral modifiers in asymmetric hydrogenation of N-
heteroaromatics. The effects of organic shell and chiral ligand
density on the reactivity and enantioselectivity were explained
by 31P-NMR spectroscopy and experimental facts. With the
appropriate ratios of Bin-PdNPs and chiral phosphine ligands
used, asymmetric hydrogenations of 2-substituted quinolines
and 2-arylindoles were achieved with good to excellent yields
and moderate enantioselectivities, which showed superiority
to that of palladium complex. Further application of this
protocol into other asymmetric reactions is ongoing in our
laboratory.
,
T. Nguyen, A. Meier, D. H. Hua, J. Am. Chem. Soc. 2016, 138
16839.
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This project is supported by the National Natural Science
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