New Catalysts for Asymmetric Synthesis

Modified Asymmetric Transfer
Hydrogenation Catalysts& Triflate Catalysts
Product Outline
Modified Asymmetric Transfer Hydrogenation Catalysts
Prototype Catalysts (S,S)-form
R
N

Modified Catalysts (S,S)-form
R
N

R'n
Ru

N
H2
R: SO2C6H4-p-CH3 (Ts)
SO2CH3 (Ms)

R'n
Ru

N
H2

Cl
R'n : 1-CH3-4-CH(CH3)2
1,3,5-(CH3)3
1,2,3,4,5,6-(CH3)6

R: BnSO2

2',6'-(CH3)2BnSO2

Cl
R'n : 1-CH3-4-CH(CH3)2

i-BuSO2

1,3,5-(CH3)3

Cs (camphor sulfonyl)

KANTO CHEMICAL CO., INC. launched asymmetric transfer hydrogenation catalysts with
Ts-diamine ligand, which were discovered by NOYORI Molecular Catalysis Project of Exploratory Research for Advanced Technology (ERATO) by Japan Science and Technology Corporation(JST). These catalysts are extremely effective ones for the asymmetric reduction of ketones andimines, and have established their reputation as conventional effective asymmetric reduction catalysts.
A research group of KANTO CHEMICAL CO., INC. examined the reaction conditions toachieve the maximum catalyst performance, and found out that a choice of the hydrogen source isthe most important to achieve the higher reactivity and the enantioselectivity.
It was reported that the reaction in a mixture of formic acid and triethylamine is the irreversible reaction, leading to the high efficiency1. We revealed that a molar ratio of formic acid andtriethylamine is important for the reaction of nitrogen-functionalized acetophenones2.
Then, it was reported that two phase reaction comprised of ketone and water (if necessary solvent is added) using sodium formate as a hydrogen source gives higher reactivity3. We developed
this reaction system to the synthesis of some chiral compounds. In this two phase reaction, a dropof enantioselectivity is often observed for the reaction of a certain kind of ketones4. Based on the
hypothesis that near the end of the reaction, the catalyst abstracts hydrogen from the product alcohol, leading to the drop of the optical purity of the product, the single phase reaction was developed by our group using formic acid salt as a hydrogen source. In the single phase reaction, thehigh reactivity is maintained with little drop of the optical purity of the product alcohol.
In terms of the modification of the catalysts, easily tunable sulfonyl group affects the enantioselectivity of the reaction, and we, launches modified Ru catalysts with higher catalyst performance.

Triflate Catalysts
Asymmetric Transfer Hydrogenation Catalysts（Chloro Complexes） (S,S)-form

Asymmetric Hydrogenation Catalysts（Triflate Complexes） (S,S)-form

Ts

Ts
N

N
Ru

Ru
N
H2

N
H2

Cl

OTf

RuCl(Tsdpen)(arene) catalyst is an excellent asymmetric reduction catalyst using a kind oforganic hydrogen source, but this catalyst can’t use hydrogen gas. In the project in Chubu Technology Licensing Office of Nagoya Industrial Science Research Institute directed by Prof. Ryoji
Noyori of Nagoya University and Prof. Takeshi Ohkuma of Hokkaido University, the asymmetrichydrogenation catalyst using hydrogen gas was developed, which has a similar structure to theabove mentioned reduction catalyst5.
Because this asymmetric hydrogenation reaction proceeds without a base, this reaction system isapplicable to the base sensitive ketones. For example, 4-chromanone is reduced in a mixture of
formic acid and triethylamine with 97% ee, but in low yield 37% at S/C (substrate/catalyst molar
ratio) of 500. In contrast, in this asymmetric hydrogenation reaction, 4-chromanoe is reduced
completely even at S/C = 30005a, and the ton (turn over number) over 7000 can be obtained undera higher hydrogen pressure.
KANTO CHEMICAL CO., INC., launches chiral Ru Triflate asymmetric hydrogenation catalysts. Please refer to the section 2 (asymmetric hydrogenation of ketones).

1

Asymmetric Transfer Hydrogenation of Ketones

1-1 Choice of the Hydrogen Source
The choice of the hydrogen source is the first concerning point. The reaction in 2-propanol isa reversible reaction, and the limited efficiency (low concentration of the ketones and the moderate
reactivity) is obtained. Although, in case of the reaction of the α,β-acetylenic ketones, 2-propanol isreported to be the best choice1e.
OOHchiral Ru cat

C6H5

2-propanol
28 ºC, 20 h

S/C = 200
[ketone] = 0.1 mol/Lchiral Ru cat:Ru[(S,S)-Tsdpen](p-cymene)

C6H5
99% yield, 97% ee

The reaction efficiency is largely improved by the reaction in a mixture of formic acid andtriethylamine than that in 2-propanol. Solvent can be added when the solubility of the ketone is notenough. The molar ratio of formic acid to triethylamine determines the result. For example, in caseof the nitrogen-functionalized ketones, α-cyano acetophenone is reduced in the presence of chiral Ru
catalyst at the selected conditions (formic acid/triethylamine/ketone = 3.1:2.6:1.0) to give chiral cyano
alcohol quantitatively with 98% ee2, but no reaction with the standard conditions (formic acid/triethylamine/ketone = 5.0:2.0:1.0).
OH

O
X

X

chiral Ru cat
HCO2H/N(C2H5)330 °C, 24 h

X = CN, N3, NO2chiral Ru cat: RuCl[(S,S)-Tsdpen](p-cymene)
X

S/C

CN

1000

5/2/1

24

0

-

-

CN

1000

3.1/2.6/1

24

100

98

S

N3

100

3.1/2.6/1

24

65

92

R

NO2a

200

6.0/2.4/1

16

90

98

R

HCO2H/N(C2H5)3/ketone time, hyield, %ee, % config

a[ketone] = 1.0 mol/L in dmf.
0

The reaction of racemic-benzoin is useful for the production of chiral hydrobenzoin6 indicates thatthe reaction in a mixture of formic acid and triethylamine is suitable for the asymmetric reaction witha dynamic kinetic resolution.
OH

Ochiral Ru cat

C6H5

C6H5

C6H5

HCO2H/N(C2H5)3dmf
40 ºC, 24 h

OH

C6H5
OH
>99% yield
syn/anti = 98:2
>99% ee

S/C = 1000
chiral Ru cat: RuCl[(S,S)-Tsdpen](p-cymene)

In 2004, it was reported that the two phase reaction comprised of acetophenone and water using
sodium formate as a hydrogen source proceeds effectively3. In the reaction of acetophenone with amixture of formic acid and triethylamine, only 1 % conversion is obtained at 0.5 h, but 76 % conversion is obtainable in two phase reaction using sodium formate at the same reaction time.
OH

O
C6H5

+

hydrogensourcechiral Ru cat

40 ºC
chiral Ru cat: RuCl[(S,S)-Tsdpen](p-cymene),
S/C = 100.
hydrogensourceHCO2H/N(C2H5)3
HCO2Natime, hconv, %

ee, %

0.5

1

>99

12

98

97

0.5

76

95

C6H5

As mensioned above, the two phase reaction is a high speed reaction. Liquid ketones can be reducible
without an added solvent and this reaction is successfully applied to the preparation of chiral 1,1,1trifluoro-2-propanol, which has low boiling point (79 oC) and high solubility to the water. In fact, 1,1,1trifluoroacetone is reduced in the presence of RuCl[(S,S)-Tsdpen](mesitylene) effectively to yield (S)1,1,1-trifluoro-2-propanol in 97% ee quantitatively. The organic phase comprised of the crude alcohol
without any solvents is easily purified by easy operations (drying, and simple distillation) to give the (S)1,1,1-trifluoro-2-propanol, 97% ee in high isolated yield.
O
+

F3C

HCO2K

H2O, 30

o

O

CF3

N

F 3C

C, 24 hup to S/C = 1000
chiral Ru cat: RuCl[(S,S)-Tsdpen](mesitylene)O

OH

chiral Ru cat

N

Water soluble,
b.p. 79 oC
100% yield, 97% ee

F3C

Ms

F

Medicine for dementia, mania and depression

Two phase reaction has a high reactivity, but a small drop of enantioselectivity is observed in somecases. Time course study revealed that the optical purity of the product alcohol decreases to some extent. In case of a certain ketonic substrates, several % drop of optical purity is observed. Reaction
with low speed stirring also enhanses the racemization. The insufficient supply of the hydrogen source(present in water phase) to the catalyst (present in organic phase) is assumed to cause the racemizationof alcohol4.
To solve the intrinsic nature of the two phase reaction, we developed the effective single phase reaction. High efficiency is maintained using formic acid salt as a hydrogen source, and suppresses the racemization of the product alcohol in this single phase reaction.
For example, 4-chromanone is reduced in the presense of RuCl[(S,S)-Tsdpen](p-cymene) to give the(S)-4-chromanol with 99% ee quantitatively in single phase reaction. Phenacyl chloride is also reduced
to give (R)-1-phenyl-2-chloroethanol with 98% ee, which is an important chiral building block. As
shown above, single phase reaction using formic acid salt with chiral Ru catalyst gives chiral alcoholwith high enantioselectivity and high yield.
O

OH+(S,S)-Ru cat

HCO2K

CH3OH
50 oC, 24 h

O

OH

OH
Cl

98% eeO
100% yield, 99% ee
OHOH

95% eeOH
CN

95% eeOH
CO2CH397% eeOH

93% eeConditions: S/C = 1000, 50 oC, 24 h, 100% yield.
(S,S)-Ru cat: RuCl[(S,S)-Tsdpen](p-cymene)

1-2. Asymmetric Transfer Hydrogenation with Modified Chiral Ru Catalysts
Arene ligand, diamine ligand, and sulfonyl group are tunable parts in these chiral Ru catalysts.
Modified chiral Ru catalysts on sulfonyl group have higher enantioselectivity for the reaction of a certain ketones. For example, the eantioselectivity of the reduction of 3’,5’-bis(trifluoromethyl)acetophenone is influenced by the structure of the catalyst in two phase reaction with sodium formate
as a hydrogen source. Chiral Ru catalyst with benzylsulfonyl group, or 2’,6’-dimethylbenzylsulfonylgroup has higher enantioselectivity for the reaction of 3’,5’-bis(trifluoromethyl)acetophenone than prototype TsDPEN catalyst, leading to (S)-1-[3’,5’-bis(trifluoromethyl)phenyl]ethanol with 95-97% ee’s.
As no racemization is observed in this two phase system (discussed above), the modified Ru catalyst improves the enantioselectivity.

CF3
O

modifiedchiral Ru cat

F 3C

F 3C

HCO2K/H2Oo
50 C, 24 h

CF3
S/C = 5000

H3 C

OH

CF3
O

CF3

NH2

e
n
i
a
r
g
i
m
d
n
a
s
i
s
e
m
e
,
a
m
h
t
s
A
r
o
f
e
n
i
c
i
d
e
M

Receptor of antagonise Tachykinin

areneyield, %

ee, %

Ts

p-CYMENEa

82

80.9

BnSO2

p-CYMENE
MESITYLENEb

2',6'-(CH3)2BnSO2

p-CYMENE
MESITYLENE

90.7
94.9
95.9
96.8

i-BuSO2

p-CYMENE
MESITYLENEc

94
89
100
83
100
100

90.5
83.1

(S)-Csp-CYMENE

92

75.5

R
modified chiral Ru cat

R'n

R
N

Ph

Ru
Ph

N
H2

Cl

RuCl[(S,S)-Rdpen](arene)a

S/C = 3000, bS/C = 4000, cS/C = 2000.

Chiral Ru catalysts with Cs-sulfonyl group7 have higher enantioselectivity for a kind of ketones
as shown below.
O

Ph

R
N

O

Cl
Ru

Ph

O

N
H2

Cl
Cl

RuCl[(S,S)-Rdpen](p-cymene)Ryield, %, ee, %a

Ts
BnSO2
i-BuSO2(S)-Cs77, 91.3
60, 93.4
82, 93.3
83, 95.5

yield, %, ee, %b85, 90.0100, 94.3
94, 93.8
98, 95.8

yield, %, ee, %c
88, 81.5
99, 90.7
97, 91.4
97, 94.9

HCO2K in water, aS/C = 7000, bS/C = 5000, cS/C = 1000.

2

Asymmetric Hydrogenation of Ketones

Chiral Ru complexes with diphosphine and diamine ligand, such as RuCl2(binap)(dpen)8 have highreputation as asymmetric hydrogenation catalysts for ketones, and KANTO CHEMICAL CO., IMC.
launched these complexes. Since the real catalyst is in situ prepared by mixing pre-formed Ru complex
and a strong base such as KO-tBu in this reaction, base sensitive ketones are not often applicable withthis catalyst system.
In the point of the mechanism, RuCl(Tsdpen)(p-cymene) with Ts-diamine ligand, although they havestructural similarity to RuCl2(binap)(dpen), have high catalytic activity for the reduction of ketones using organic hydrogen source such as 2-propanol and formic acid, can not activate hydrogen gas. Newly
developed Ru(OTf)(Tsdpen)(p-cymene), which has a dissociative anionic OTf group, can hydrogenate
ketones using hydrogen gas in methanol without a base5.

This catalyst is applicable to a kind of base sensitive ketones, which can not be hydrogenated withthe previous hydrogenation catalysts effectively. For example, 4-chromanone is a base sensitive substrate, and a limited example was reported for the asymmetric hydrogenation of this compound9.
4-Chromanone is hydrogenated with Ru(OTf)[(S,S)-Tsdpen](p-cymene) catalyst even at S/C = 3000
(conditions: 60 oC, 15 h) to give (S)-4-chromanol with 97% ee quantitatively5a.
OHO+

10 atmH2chiral Ru cat
CH3OH
60 oC, 15 h

O
S/C = 3000
up to 7000

O
100% yield, 97% eechiral Ru cat:Ru(OTf)[(S,S)-Tsdpen](p-cymene)

OH

OH
Cl

TfO

Ru

O

O

95% yield, 98% ee

100% yield, 98% ee(S/C = 1000)

NTs

H2N

Ph

(S/C = 1500)

PhThis catalyst is also applicable to a variety of base sensitive ketones. For example, phenacyl chloride ishydrogenated with Ru(OTf)[(S,S)-Tsdpen](p-cymene) to yield (R)-2-chloro-1-phenylethanol with 98%
ee at S/C of 10005b. Phenacyl chlorides with electron donating substituent such as methyl group andmethoxy group, and those with electron withdrawing group such as chloro and trifluoromethyl group,
are also hydrogenated effectively to give the chlorophenylethanols with high ee’s. Phenacyl chloride
with non protected phenolic hydroxyl group, can be hydrogenated to give chiral chlorophenylethanol,
which is derived to (R)-norphenylephrine in two steps.
OHO
10 atm
H2

Cl
+

Cl

Ru(OTf)[(S,S)-Tsdpen](mesitylene)
CH3OH
60 °C, 15 h

S/C = 1000
up to 4000

OH

>99% yield, 98% ee

OH

OH
Cl

Cl

Cl
CH3O

96% ee
OH

OH

OH
Cl

Cl

Cl
95% ee

OH
Cl

Cl

F3C

Cl

Cl
94% eeOH

94% ee96% eeOH

Cl
CH3O2C

95% ee95% eeHOCl

98% ee1) NaN3
2) H2, Pd/C

96% eeOH
HONH2(R)-Norphenylephrine

3

References and Patents

A．References
1 (a) Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 7562.
(b) Fujii, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 2521.
(c) Uematsu, N.; Fujii, A.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1996, 118, 4916.
(d) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97.
(e) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1997, 119, 8738.
(f) Watanabe, M.; Murata, K.; Ikariya, T. J. Org. Chem. 2002, 67, 1712.
(g) Murata, K.; Okano, K.; Miyagi, M.; Iwane, H.; Noyori, R.; Ikariya, T. Org. Lett. 1999, 1, 1119.
(h) Ikariya, T.; Murata, K.; Noyori, R. Org. Biomol. Chem. 2006, 4, 393.
(i) Ikariya, T.; Blacker, A. J. Acc. Chem. Res. 2007, 40, 1300.
2 Watanabe, M.; Murata, K.; Ikariya, T. J. Org. Chem. 2002, 67, 1712.
3 Wu, X.; Li, X.; Hems, W.; King, F.; Xiao, J. Org. Biomol. Chem. 2004, 2, 1818.
4 Murata, K. P41 Novel Chiral Chemistry Japan (2009)
5 (a) Ohkuma, T.; Utsumi, N.; Tsutsumi, K.; Murata, K.; Sandoval, C.; Noyori, R. J. Am. Chem. Soc. 2006, 128, 8724.
(b) Ohkuma, T.; Tsutsumi, K.; Utsumi, N.; Arai, N.; Noyori, R.; Murata, K. Org. Lett. 2007, 9, 255.
(c) Sandoval, C. A.; Ohkuma, T.; Utsumi, Tsutsumi, Murata, K, Noyori, R. Chem. Asian. J. 2006, 1-2, 102.
6 Murata, K.; Okano, K.; Miyagi, M.; Iwane, H.; Noyori, R.; Ikariya, T. Org. Lett. 1999, 1, 1119.
7 Cs catalyst Li, X.; Blacker, J.; Houson, I.; Wu, X.; Xiao, J. Synlett 2006, 1155.など
8 (a) Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 2675.
(b) Ohkuma, T.; Ooka, H.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 10417.
(c) Doucet, H.; Ohkuma, T.; Murata, K.; Yokozawa, T.; Kozawa, M.; Katayama, E.; England, A. E.; Ikariya, T.; Noyori, R.
Angew. Chem. Int. Ed. Engl. 1998, 37, 1703.
(d) Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. Engl. 2001, 40, 40.
9 Zhang, X.; Takemoto, T.; Yoshizumi, T.; Kumobayashi, H.; Akutagawa, S.; Mashima, K.; Takaya, H. J. Am. Chem. Soc.
1993, 115, 3318.

B．Patents
1. Preparation of optically active alcohols 2962668 (Japan)
2. Ruthenium complexes with diamine ligands and preparation of optically active alcohols withthese catalysts 3040353 (Japan)
3. Preparation of optically active 1,2-diols 3630002 (Japan)
4. Chiral catalysts and preparation of optically active alcohols with these catalysts 2010-248091 (Japan)
5. Preparation of optically active alcohols 2010-111120 (Japan)
6. Preparation of optically active aliphatic fluoro-alcohols 2010-1462190 (Japan)
7. Sulfonate catalysts and preparation of optically active alcohols with these catalysts WO2006-137195

4

Custom Synthesis, Process Development

KANTO CHEMICAL CO., INC. supplys suitable catalyst for your substrates, and has kowhows such as the choice of the hydrogen source and the reaction conditions. Please consult us
about the usage of these chiral reduction catalysts and the optimization of the reaction conditions. We also develop the asymmetric reduction process with these catalysts and apply to custom synthesis.

Product List
Modified Asymmetric Transfer Hydrogenation Catalysts
Product Name

Product Number Package Size

Chloro[(1R,2R)-N-(isobutanesulfonyl)-1,2diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(R,R)-i-BuSO2dpen](p-cymene)

C28H36ClN2O2RuS
F.W : 601.29

Chloro[(1S,2S)-N-(isobutanesulfonyl)-1,2diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(S,S)-i-BuSO2dpen](p-cymene)

C28H36ClN2O2RuS
F.W : 601.29

Chloro[(1R,2R)-N-(isobutanesulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(II)

RuCl[(R,R)-i-BuSO2dpen](mesitylene)

C27H34ClN2O2RuS
F.W : 587.16

Chloro[(1S,2S)-N-(isobutanesulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(II)

RuCl[(S,S)-i-BuSO2dpen](mesitylene)

F.W : 587.16

F.W : 695.30

C34H42ClN2O3RuS
F.W : 695.30

Chloro[(1R,2R)-N-(benzylsulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(R,R)-BnSO2dpen](p-cymene)

C30H32ClN2O2RuS
F.W : 621.18

Chloro[(1S,2S)-N-(benzylsulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(S,S)-BnSO2dpen](p-cymene)

C30H32ClN2O2RuS
F.W : 621.18

Chloro[(1R,2R)-N-(benzylsulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(Ⅱ)

RuCl[(R,R)-BnSO2dpen](mesitylene)

C29H30ClN2O2RuS
F.W : 607.15

Chloro[(1S,2S)-N-(benzylsulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(Ⅱ)

RuCl[(S,S)-BnSO2dpen](mesitylene)

07710-65

1g

07711-95

200mg

07711-651g

07721-95

200mg

07721-651g07722-95

200mg

07722-651g07715-95

200mg

07715-651g07716-95

200mg

07716-651g07717-95

200mg

07717-651g07718-95

200mg

07718-651g07719-95

200mg

07719-651g07720-95

200mg

07720-65

1g

C34H42ClN2O3RuS

Chloro{(1S,2S)-N-[(1S)-camphorsulfonyl]-1,2diphenylethanediamine}(p-cymene)ruthenium(Ⅱ)

RuCl[(S)-Cs-(S,S)dpen](p-cymene)

200mg

C27H34ClN2O2RuS

Chloro{(1R,2R)-N-[(1R)-camphorsulfonyl]-1,2diphenylethanediamine}(p-cymene)ruthenium(Ⅱ)

RuCl[(R)-Cs-(R,R)dpen](p-cymene)

07710-95

C29H30ClN2O2RuS
F.W : 607.15

Product Name

Product Number Package Size

Chloro[(1R,2R)-N-(2’,6’-dimethylbenzylsulfonyl)-1,2diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(R,R)-2’,6’-(CH3)2BnSO2dpen](p-cymene)

F.W : 649.23

F.W : 649.23

1g07735-95

200mg

07735-651g07736-95

200mg

07736-651g07737-95

200mg

07737-65

1g

C31H34ClN2O2RuS
F.W : 635.20

Chloro[(1S,2S)-N-(2’,6’-dimethylbenzylsulfonyl)-1,2diphenylethanediamine](mesitylene)ruthenium(Ⅱ)

RuCl[(S,S)-2’,6’-(CH3)2BnSO2dpen](mesitylene)

07734-65

C32H36ClN2O2RuS

Chloro[(1R,2R)-N-(2’,6’-dimethylbenzylsulfonyl)-1,2diphenylethanediamine](mesitylene)ruthenium(Ⅱ)

RuCl[(R,R)-2’,6’-(CH3)2BnSO2dpen](mesitylene)

200mg

C32H36ClN2O2RuS

Chloro[(1S,2S)-N-(2’,6’-dimethylbenzylsulfonyl)-1,2diphenylethanediamine](p-cymene)ruthenium(Ⅱ)

RuCl[(S,S)-2’,6’-(CH3)2BnSO2dpen](p-cymene)

07734-95

C31H34ClN2O2RuS
F.W : 635.20

Triflate Catalysts
Product Name

Product Number Package Size[(1R,2R)-N-(p-toluenesulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(Ⅱ) triflate

Ru(OTf)[(R,R)-Tsdpen](p-cymene)

C32H35F3N2O5RuS2
F.W : 749.83[(1S,2S)-N-(p-toluenesulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(Ⅱ) triflate

Ru(OTf)[(S,S)-Tsdpen](p-cymene)

C32H35F3N2O5RuS2
F.W : 749.83

41068-95

200mg

41068-651g41069-95

200mg

41069-65

1g

Related ProductPrototype Asymmetric Transfer Hydrogenation Catalysts
Product Name
Chloro[(1R,2R)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

RuCl[(R,R)-Tsdpen](p-cymene)
Chloro[(1S,2S)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

RuCl[(S,S)-Tsdpen](p-cymene)
Chloro[(1R,2R)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(II)

RuCl[(R,R)-Tsdpen](mesitylene)
Chloro[(1S,2S)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](mesitylene)ruthenium(II)

RuCl[(S,S)-Tsdpen](mesitylene)
Chloro[(1R,2R)-N-(methanesulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

RuCl[(R,R)-Msdpen](p-cymene)
Chloro[(1S,2S)-N-(methanesulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

RuCl[(S,S)-Msdpen](p-cymene)[(1R,2R)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

Ru[(R,R)-Tsdpen](p-cymene)[(1S,2S)-N-(p-toluensulfonyl)-1,2-diphenylethanediamine](p-cymene)ruthenium(II)

Ru[(S,S)-Tsdpen](p-cymene)

Product Number

Package Size

08154-95

200mg

08154-651g08153-95

200mg

08153-651g08173-95

200mg

08173-651g08174-95

200mg

08174-651g08175-95

200mg

08175-651g08176-95

200mg

08176-65

1g

41066-95

200mg

41066-651g41067-95

200mg

41067-65

1g

Product Number

Package Size

Prototype Asymmetric Hydrogenation Catalysts
Product Name
Dichloro[(R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(R,R)-1,2-diphenylethanediamine]ruthenium(II)

RuCl2[(R)-binap][(R,R)-dpen]
Dichloro[(R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(S,S)-1,2-diphenylethanediamine]ruthenium(II)

RuCl2[(R)-binap][(S,S)-dpen]
Dichloro[(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(R,R)-1,2-diphenylethanediamine]ruthenium(II)

RuCl2[(S)-binap][(R,R)-dpen]
Dichloro[(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(S,S)-1,2-diphenylethanediamine]ruthenium(II)

RuCl2[(S)-binap][(S,S)-dpen]

11404-95

200mg

11404-65

1g11405-95

200mg

11405-65

1g11402-95

200mg

11402-65

1g11403-95

200mg

11403-65

1g

Product Name

Product Number

Package Size

11408-95

200mg

11408-65

1g11409-95

200mg

11409-65

1g

Product Number

Package Size

10535-68

100mg

10535-95

500mg

10537-68

100mg

10537-95

500mg

10536-68

100mg

10536-95

500mg

10538-68

100mg

10538-95

500mg

Product Number

Package Size

08288-55

5g08288-35
08347-55

25g
5g

08347-35

25g

18617-55

5g

18617-35

25g

18618-55

5g

18618-35

25g

20318-651g20318-35

25g

20342-651g20342-3525g(R)-(+)-Phenylethanol

32123-35

25g(S)-(+)-Phenylethanol

32124-35

25g

Dichloro[(R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(R)-1,1-bis(p-methoxyphenyl)-2-isopropylethane-1,2-diamine]ruthenium(II)

RuCl2[(R)-binap][(R,R)-daipen]
Dichloro[(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl][(S)-1,1-bis(p-methoxyphenyl)-2-isopropylethane-1,2-diamine]ruthenium(II)

RuCl2[(S)-binap][(S,S)-daipen]

Highly Selective Hydrogenation Catalysts
XylSKEWPHOS Catalysts
Product Name
Dibromo[(R,R)-2,4-bis(di-3’,5’-xylylphosphino)pentane][(R,R)-1,2-diphenylethanediamine]ruthenium(Ⅱ)

RuBr2[(R,R)-xylskewphos][(R,R)-dpen]
Dibromo[(R,R)-2,4-bis(di-3’,5’-xylylphosphino)pentane][(S)-1,1-bis(p-methoxyphenyl)-2-isopropyl-1,2-ethanediamine]-ruthenium(Ⅱ)

RuBr2[(R,R)-xylskewphos][(S)-daipen]
Dibromo[(S,S)-2,4-bis(di-3’,5’-xylylphosphino)pentane][(S,S)-1,2-diphenylethanediamine]ruthenium(Ⅱ)

RuBr2[(S,S)-xylskewphos][(S,S)-dpen]
Dibromo[(S,S)-2,4-bis(di-3’,5’-xylylphosphino)pentane][(R)-1,1-bis(p-methoxyphenyl)-2-isopropyl-1,2-ethanediamine]ruthenium(Ⅱ)

RuBr2[(S,S)-xylskewphos][(R)-daipen]

Chiral Alchols
Product Name(R)-4-Chromanol(S)-4-Chromanol(R,R)-(+)-Hydrobenzoin(S,S)-(-)-Hydrobenzoin(R)-(-)-1-Indanol(S)-(+)-1-Indanol

Product Name

Product Number

Package Size(R)-1,1,1-Trifluoro-2-propanol

41181-35

25g(S)-1,1,1-Trifluoro-2-propanol

41182-35

25g

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Product Number

Package Size(R)-1-[3,5-Bis(trifluoromethyl)phenyl]ethanol(S)-1-[3,5-Bis(trifluoromethyl)phenyl]ethanol

Metal Scavenger (R-Cat-Sil)
Product Name
R-Cat-Sil AP
Loading : 2.0mmol/g<Metals removed>
Pd, Ru, Rh, Co,
Cu, Fe, Ni

Si

NH2

R-Cat-Sil MP
Loading : 1.2mmol/g<Metals removed>
Pd, Ru, Rh, Cu,
Pt, Pb, Ag, Hg

SiSH

R-Cat-Sil TA
Loading : 1.0mmol/g<Metals removed>
Pd, Rh, Co, Cu,
Fe, Zn, Pt

Si

N
H

H
N

2

＜Reference Data＞Particle size：50μm、Specific surface：730m /g

NH236044-555g

36044-3525g

36044-25100g

36045-555g

36045-3525g

36045-25100g

36046-555g

36046-3525g

36046-25100g