(2.8MB/16p)

INDEX
A. Immobilized Catalysts
1 Chemoselective Reduction Catalysts
    <Os/C; 5% Pd/Cn(en); 10% Pd/C(en); Pd/Fib; Pd/PEI>
2 Calcium Vanadate Apatite <VAP>
3 HAP-supported Catalysts <RuHAP-Fe2O3, RuHAP>
4 Multimetallic Concerto Asymmetric Catalyst
    <Homodinuclear Ni2-Schiff Base Catalyst>
B. Chiral Ligands
1 Ligands for Catalytic Asymmetric Synthesis <Linked-BINOL>
2 Bisphosphoramidite Chiral Ligands <Me-BIPAM>
3 Iodine-containing BINAP <5,5'-Diiodo BINAP Dioxide>
C. Metal Catalysts
1 ZACA Reagents for metal-catalytic asymmetric synthesis
D. Organic Molecular Catalysts
1 Maruoka Catalysts <Chiral Phase-Transfer Catalysts (PTC)>
2 Kawabata Acylation Catalyst <Chemo- & Regioselective Acylation>
3 Catalysts for Alcohol Oxidation <1-Me-AZADO>
E. Fluorous Reagents
1 Medium Fluorous Mukaiyama Reagent
2 Fluorinating Agents <DAST, BAST >
F. Cyclic Triolborates




    Alphabetical Index
Description
A (2-Acetamidophenyl) cyclic triolborate Potassium Salt
2-Azaadamantane-N-oxyl
AZADO
B BAST
1,1'-Bi-2-naphthol
(2-Biphenyl)cylclic-triolborate Potassium Salt
2,2'-Bis(diphenyl phosphino)-1,1'-binaphthyl
2,2'-Bis(diphenylphosphino)-5,5'-diiodo-1,1'-binaphthyl
3,5-Bistrifluoromethylpheny-NAS Bromide
Bis[1-(2-iso-propyl-5'-methylcyclohexyl)indenyl]zirconium (IV) Dichloride
Bis(2-methoxyethyl) aminosulfur Trifluoride
3,5-Bistrifluoromethylphenyl-NAS Bromide
C Calcium Vanadate Apatite
Chemoselective Reduction Catalyst Set
Chiral Phase-Transfer Catalyst
2-Chloro-1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyl) pyridinium Trifuoromethanesulfonate
2-Chloro-1-(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoroundecyl)pyridinium
D DAST
Diethylaminosulfur Trifluoride
5,5'-Diiodo-BINAP Dioxide
1,2-Diphenylethylenediamine
F (2-Formylphenyl) cyclic-triolborate Sodium Salt
(2-Formyl-3-thiophene) cyclic-triolborate Potassium Salt
H Homodinuclear Ni2-Schiff Base Catalyst
K Kawabata Acylation Catalyst
L Light Fluorous Mukaiyama Reagent
Linked-BINOL
Description
M Maruoka Catalyst
1-Me-AZADO
Me-BIPAM
Medium Fluorous Mukaiyama Reagent
1-Methyl-2-azaadamantane-N-oxyl
N (1-Naphthalene)cyclic-triolborate Potassium Salt
(NMI)2ZrCl2
O Os/C
Osmium-Activated Carbon (Os 3.5%-6.5%)
3,3"-[Oxybis(methylene)]-1,1'-bi-2-naphthol
P Palladium-Activated Carbon Ethylenediamine Complex (Pd 3.5~6.5%) or (Pd 8.5~11.5%)
Palladium-Fibroin
Palladium-Polyethyleneimine
5% Pd/C(en) or 10% Pd/C(en)
Pd/Fib
Pd/PEI
(2-Pyridine)cyclic-triolborate Lithium Salt
2',5'-[4-(N-Pyrrolidinyl)pyridine]bis[2-acetylamido)-e-(1H-indol-3-yl)]propioniuc Acid Octyl Ester
R RuHAP
RuHAP-Fe2O3
Ruthenium (III) Hydroxyapatite
Ruthenium (III)-Hydroxyapatite Encapsulated Superparamagnetic Maghemite
T (2,5-Thiophene) dicyclic-triolborate Dipotassium Salt
3,4,5-Trifluoropheny-NAS Bromide
V VAP
W Wakopak® Fluofix®-II 120E
Z ZACA reagent

    Index by Reaction
Type Reaction Metal Chemical compounds used in the reaction
Reduction Catalytic Reduction Os Os/C
Pd Pd/C(en)
Pd Pd/Fib
Pd Pd/PEI
Pd PI/Pd
Oxidation Alcohol Oxidation - AZADO
- 1-Me-AZADO
Ru Ru HAP-Encapsulated Superparamagnetic Maghemaite
Ru Ru-HAP
Silane Oxidation Ru Ru-HAP
Coupling Suzuki-Miyaura Coupling Reaction - Cyclic-triolborate
ZACA Reaction ZACA Reaction Zr (NMI)2ZrCl2
Deuteration - V VAP
Hydration Nitrile Hydration Ru Ru-HAP
Asymmetric Reaction - Allylic Amination Reaction Pd Me-BIPAM, Pd Catalyst
- Aldol Reaction - Linked-BINOL
Zr Chiral Phase-Transfer Catalyst (Maruoka Catalyst)
- Carboalumination Zr (-)-(NMI)2ZrCl2
- Carboalumination Zr (+)-(NMI)2ZrCl2
- Conjugate Addition Reaction - Me-BIPAM
- Hydrogenation Reaction Rh Me-BIPAM, Rh Catalyst
- Mannich Reaction - Linked-BINOL
- Mannich Reaction Ni Homodinuclear Ni2-Schiff Base Catalyst
- Michael Reaction - Linked-BINOL
Acylation Reaction - Catalytic one-step reaction - Kawabata Acylation Catalst
Other - - Fluorous Mukaiyama Reagent
For other products, please visit the Wako Online Catalog www.e-reagent.com


A-1 Chemoselective Reduction Catalysts <Os/C; 5% Pd/Cn(en); 10% Pd/C(en); Pd/Fib; Pd/PEI>
In catalytic reduction, palladium-carbon (Pd/C), a heterogeneous catalyst, is widelyused since it can effectively reduce various functional groups under mild neutralconditions. By Pd/C, however, chemoselectivity or regioselectivity cannot be achieved due to the strong reducing ability. To solve these problems, Wako provides fixed catalysts which have chemoselectivity by using ethylenediamine (abbreviated product name [Pd/C (en)] 1)), fibroin (abbreviated product name [Pd/Fib] 2)), or polyethyleneimine (abbreviated product name [Pd/PEI] 3)) as a catalyst poison.
In addition to the above, osmium-activated carbon, a complex of osmium with activated carbon, shows different selectivity (reduction of aromatic nitro groups prior to olefins) from the existing palladium catalysts.
Wako has just released these 5 selective reduction catalysts in a kit. You can choose the catalyst of interest by comparing these catalysts with various activities.
■ Palladium-Activated Carbon Ethylenediamine Complex [Pd/C(en)]
1) Chemoselective reduction catalyst in which ethylenediamine is coordinated to Pd/C.
2) The remaining catalysts can be readily removed by filtration after the reaction.
3) Unlike the general Pd/C, it is not combustible and has good storage stability.
■ Palladium-Fibroin [Pd/Fib]
1) Approximately 2.5% Pd is supported on silk fibroin.
2) The remaining catalysts can be readily removed by filtration after the reaction.
3) It can inhibit degradation of the functional groups susceptible to hydrogen
reduction reaction more efficiently than Pd/C(en).
■ Palladium-Polyethyleneimine [Pd/PEI]
1) Polyethyleneimine polymer is used as a carrier.
2) It can catalyze a selective partial hydrogenation from alkines to alkenes.
■ Osmium-Activated Carbon [Os/C]
1) It selectively reduces aromatic nitro groups.
2) Less combustible.
3) New type catalyst which is not a toxic and volatile osmium tetroxide.
[References]
1) H. Sajiki, K. Hattori, K. Hirota : J. Org. Chem., 63, 7990 (1998).
2) H. Sajiki, T. Ikawa, H. Yamada, K. Tsubouchi, K. Hirota : Tetrahedron Lett., 44, 171 (2003).
3) H. Sajiki, S. Mori, T. Ohkubo, T. Ikawa, A. Kume, T. Maegawa, Y. Monguchi : Chem. Eur. J., 14, 5109 (2008).
Description Grade Wako Cat. No. (Pkg. Size) Storage
Chemoselective Reduction Catalyst Set for Organic Synthesis 032-21041 (1 set) Keep at RT.
Kit Contents:

(1) Palladium-Activated Carbon Ethylenediamine Complex (Pd 3.5 ~ 6.5%) [5% Pd/C (en)] : 1 bottle x 1 g
(2) Palladium-Activated Carbon Ethylenediamine Complex (Pd 8.5 ~ 11.5%) [10% Pd/C (en)] : 1 bottle x 1 g
(3) Palladium-Fibroin [Pd/Fib]: 1 bottle x 1 g
(4) Palladium-Polyethyleneimine [Pd/PEI] : 1 bottle x 1 g
(5) Osmium-Activated Carbon (Os 3.5 ~ 6.5%) [Os/C] : 1 bottle x 1 g

Related Products
10% Pd/C(en) (Pd 8.5~11.5%)
Palladium-Activated Carbon Ethylenediamine Complex
for Organic Synthesis 163-23301 (1 g);
163-23303 (5 g)
Keep at RT.
5% Pd/C(en) (Pd 3.5~6.5%)
Palladium-Activated Carbon Ethylenediamine Complex
for Organic Synthesis 163-21441 (1 g);
169-21443 (5 g);
161-21442 (25 g)
Pd/Fib [Palladium-Fibroin] for Organic Synthesis 167-22181 (1 g);
163-22183 (5 g)
Pd/PEI [Palladium-Polyethyleneimine] for Organic Synthesis 161-22221 (1 g);
167-22223 (5 g)
Os/C (Os 3.5 ~ 6.5%) [Osmium-Activated Carbon] for Organic Synthesis 151-02881 (1 g);
157-02883 (5 g)
For other products, please visit the Wako Online Catalog www.e-reagent.com
A-2 Calcium Vanadate Apatite <VAP>
A calcium vanadate apatite (VAP) acts as a high-performance heterogeneous base catalyst for various carbon-carbon bond-forming reactions such as Michael and aldol reactions in aqueous media. No vanadium leaching was detected and the catalyst was readily recycled with no loss of activity.
In addition, when reacted with ketones in deuterium, it can effectively replace the hydrogen at an alpha position with a deuterium.
(1) Michael Reaction
(2) deuteration
[Reference]
1) T. Hara, S. Kanai, K. Mori, T. Mizugaki, K. Ebitani, K. Jitsukawa, K. Kaneda: J. Org. Chem., 71, 7455-62 (2006).
Description Wako Cat. No. (Pkg. Size)
Calcium Vanadate Apatite [VAP] 037-20751 (1 g)
033-20753 (5 g)

For other products, please visit the Wako Online Catalog www.e-reagent.com
A-3 HAP-supported Catalysts
Hydroxyapatite-bound Ru Complex catalyst <RuHAP>
This product is a ruthenium complex in which RuCl is supported on hydroxyapatite [HAP: Ca10(PO4)6(OH)2], a major component of bone or tooth. It is an excellent catalyst which can catalytically facilitate the oxidation reactions under ordinary pressure using oxygen as an oxidant.
More specifically, it can oxidize primary and secondary alcohols into aldehydes and ketones, respectively. The reactions progress in high yield even when air is used instead of oxygen. It also can convert primary amines, nitriles and silanes to the corresponding nitriles, amides, and silanols with high selectivity. It can be recovered and reused and is expected to be useful in the industrial applications. In addition, when reacted with ketones in deuterium, it can effectively replace the hydrogen at an alpha position with a deuterium.
[Reactions]
(1) Alcohol oxication
(2) Dehydrogenation of amine
(3) Hydration of nitrile
(4) Silane oxidation
[References]
  1. K. Yamaguchi, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda : "Creation of a Monomeric Ru Species on the Surface of Hydroxyapatite as an Efficient Heterogeneous Catalyst for Aerobic Alcohol Oxidation"J. Am. Chem. Soc., 122, 7144 (2000).
  2. K. Mori, K. Yamaguchi, T. Mizugaki, K. Ebitani, K. Kaneda : "The step-by-step synthesis of nicotinamide (2h) from 3-picolylamine (1h) using RuHAP catalyst has been reported", Chem. Commun., 461 (2001).
  3. K. Mori, M. Tano, T. Mizugaki, K. Ebitani, K. Kaneda : New J. Chem.,, 26, 1536 (2002).
Description Wako Cat. No. (Pkg. Size)
Ruthenium (III) Hydroxyapatite [RuHAP] 182-01851 (1 g)
188-01853 (5 g)
Ruthenium(III)-Hydroxyapatite Encapsulated Superparamagnetic Maghemite
New function, magnetic property, has been introduced into an oxidative catalyst gRuHAP (ruthenium(III) hydroxyapatite)" in which RuCl is supported on hydroxyapatite [HAP: Ca10(PO4)6(OH)2]. This product contains gFe2O3 (maghemite)", a magnetic nanoparticle, so that it can be rapidly separated and recovered by a magnet. It also shows high catalytic activity in the oxidation reaction of alcohols. It can be used for the accomplishment of environment-conscious reactions in the industry field.
Description Wako Cat. No. (Pkg. Size)
Ruthenium (III) Hydroxyapatite Ebcaosykated Superparamagnetic Maghemaite [RuHAP-Fe2O3] 187-02261 (500 mg)
For other products, please visit the Wako Online Catalog www.e-reagent.com
A-4 Multimetallic Concerto Asymmetric Catalyst
Homodinuclear Ni2-Schiff Base Catalysis
Multimetallic chiral bifunctional catalysts have been developed for stereoselective molecular transformations including enantioselective C-C bondformation.
A new bench-stable homodinuclear Ni2 -Schiff base complex promoted direct catalytic asymmetric Mannich-type reactions of α-substituted nitroacetates,β-keto esters, malonates, and β-keto phosphonates in high selectivity (up to 99% ee).
Figure 1
For aromatic and heterocyclic imines having various electronreleasing or electron-withdrawing substituents, the reaction progressed with high anti- and enantio-selectivities (entry #1-6). Even when the substituents in the α-position of nitro acetate esters were Et, n-Pr and Bn groups other than Me group, the reaction uneventfully progressed (entry #7-9). This catalytic system also provided reaction products with high anti- and enantio-selectivities in aliphatic imines that could be readily isomerized to enamides by reacting at low temperature for suppression of isomerization (entry #10-12). Furthermore, decrease in the amount of catalysts to 1 mol% did not affect yield and enantioselectivity and the reaction progressed efficiently (entry #13).
Nitro groups in the resulting products can be readily reduced at room temperature under NaBH4/NiCl2 conditions, and α, β-diamino ester was obtained in 94% yield.
■(R)-Homodinuclear Ni2-Schiff Base Catalyst ■(S)-Homodinuclear Ni2-Schiff Base Catalyst
[Reference]
  1. Chen, Z., Morimoto, H., Matsunaga, S., Shibasaki M.: gA Bench-Stable Homodinuclear Ni2Schiff Base Complex for Catalytic Asymmetric Synthesis of α-Tetrasubstituted anti-α, β-Diamino Acid Surrogates", J. Am. Chem. Soc, 130, 2170 (2008).
Description Grade Wako Cat. No. (Pkg. Size) Storage
(R)-Homodinuclear Ni2-Schiff Base Catalyst for Organic Synthesis 087-09011 (100 mg) Keep at 2~10°C
083-09013 (500 mg)
(S)-Homodinuclear Ni2-Schiff Base Catalyst 084-09021 (100 mg)
080-09023 (500 mg)
For other products, please visit the Wako Online Catalog www.e-reagent.com

For other products, please visit the Wako Online Catalog www.e-reagent.com

B-1 Ligands for Catalytic Asymmetric Synthesis <Linked-BINOL>
Linked-BINOL is a ligand that combines 2 BINOL together. Catalytic asymmetrical reaction is exhibited by inducing a metal, which acts as a Lewis acid, into this compound. Various reactions such as direct asymmetric aldol reaction with unmodified ketones, asymmetric Michael reaction of nucleophiles to unsaturated ketones, and asymmetric Mannich-type reaction to N-acylpyrroles that can be readily converted to esters can easily progress by using a BINOL complexed metal catalyst.
[Features]
Ligands for direct catalytic asymmetric aldol reaction with unmodified ketones and for the catalytic asymmetric Michael reaction.
[References]
  1. N. Yoshikawa, N. Kumagai, S. Matsunaga, G. Moll, T. Ohshima, T. Suzuki, M. Shibasaki: J. Am. Chem. Soc., 123, 2466 (2001).
  2. N. Kumagai, S. Matsunaga, N. Yoshikawa, T. Ohshima, M. Shibasaki: Org. Lett., 3, 1539 (2001).
  3. N. Kumagai, S. Matsunaga, M. Shibasaki: Org. Lett., 3, 4251 (2001).
  4. M. Shibasaki, M. Kanai, K. Funabashi: Chem. Commun., 1989 (2002).
  5. Y. S. Kim, S. Matsunaga, J. Das, A. Sekine, T. Ohshima, M. Shibasaki: J. Am. Chem. Soc., 122, 6506 (2000).
  6. S. Matsunaga, T. Ohshima, M. Shibasaki: Terathedron Lett., 41, 8473 (2000).
  7. Harada, S. et al.: Angew. Chem.Int. Ed., 44, 4365 (2005)

Description Wako Cat. No.
(Pkg. Size)
CAS No. MW Appearance Storage
3,3"-[Oxybis(methylene)] bis-(1R,1"R)-1,1'-bi-2-naphthol
[(R,R)-linked-BINOL], 90.0+ % (HPLC)
155-02421
(200 mg)
265116-85-6 614.68
(C42H30O5)
Solid RT
3,3"-[Oxybis(methylene)] bis-(1S,1"S)-1,1'-bi-2-naphthol
[(S,S)-linked-BINOL], 95.0+ % (HPLC)
152-02431
(200 mg)
336800-79-4 614.68
(C42H30O5)
For other products, please visit the Wako Online Catalog www.e-reagent.com
B-2 Bisphosphoramidite Chiral Ligands < Me-BIPAM >
Me-BIPAM (Bisphosphoramidite) is a bidentate phosphoroamidite-type chiral ligand. It gives good yield and selectivity, for example, in the asymmetric conjugate addition reaction of aryl boronic acid by using a rhodium catalyst. This ligand can be used in the optimal synthesis of target compounds.
[Reactions]

B-3 Iodine-containing BINAP <5,5'-Diiodo BINAP Dioxide>>
Me-BIPAM (Bisphosphoramidite) is a bidentate phosphoroamidite-type chiral ligand. It gives good yield and selectivity, for example, in the asymmetric conjugate addition reaction of aryl boronic acid by using a rhodium catalyst. This ligand can be used in the optimal synthesis of target compounds.

2,2'-Bis(diphenylphosphino)-5,5'-diiodo-1,1'-binaphthyl(5,5'-Diiodo BINAP Dioxide) is a compound in which iodines bind to BINAP. Due to its iodinecontaining and highly reactive properties, it can be utilized in the synthesis of various compounds with BINAP skeleton. It can be utilized in the synthesis of catalyst (metal catalyst) ligands used for asymmetric synthesis.
[Features]
  • Having BINAP structure as a basic skeleton gives high asymmetric induction ability
  • Its high reactivity provided by iodine makes it usable in various reactions
  • High activity for cross coupling reactions
  • Easy-to-use solid powder
  • High thermal and oxygen stabilities
Description Wako Cat. No. (Pkg. Size)
(R)-(-)-Me-BIPAM 139-15411 (200 mg)
(S)-(+)-Me-BIPAM 136-15421 (200 mg)
(R)-2,2'-Bis(diphenylphosphino)-5,5'-diiodo-1,1'-binaphthyl
[5,5'-Diiodo-BINAP Dioxide]
025-16461 (100 mg)
021-16463 (1 g)
(S)-2,2'-Bis(diphenylphosphino)-5,5'-diiodo-1,1'-binaphthyl
[5,5'-Diiodo-BINAP Dioxide]
022-16471 (100 mg)
028-16473 (1 g)
Related Products
(±)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl 325-91691 (1 g)
321-91693 (5 g)
(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl 328-91701 (1 g)
324-91703 (5 g)
(S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl 325-91711 (1 g)
321-91713 (5 g)
(R)-(+)-1,1'-Bi-2-naphthol 028-16071 (5 g)
026-16072 (25 g)
(S)-(-)-1,1'-Bi-2-naphthol 025-16081 (5 g)
023-16082 (25 g)
(1R,2R)-(+)-1,2-Diphenylethylenediamine 048-30611 (1 g)
044-30613 (5 g)
046-30612 (25 g)
(1S,2S)-(-)-1,2-Diphenylethylenediamine 045-30621 (1 g)
041-30623 (5 g)
043-30622 (25 g)
For other products, please visit the Wako Online Catalog www.e-reagent.com

C-1 ZACA Reagents for metal-catalytic asymmetric synthesis
ZACA reagent useful for asymmetric synthesis
(NMI)2ZrCl2 is an optically-active zirconium catalyst having neomenthyl groups. It exhibits a high activity in the asymmetric
carboalumination of terminal alkenes of alkylaluminum reagents (ZACA reaction). This reaction has the advantage that inexpensive substrates and reactants can be used. By repeating the reactions, natural products, such as vitamin E, vitamin K and phytol can be synthesized in high yield and stereoselectivity.
[Reactions]
(1) ZACA Reaction: Zr-Catalyzed Asymmetric Carboalumination of Alkenes
(2) Synthetic method of deoxypolypropionate from styrene 1)
(3) ZACA-lipase catalyzed acetylation 2)
[References]
  1. Novak, T. et al.: "All-Catalytic, Efficient, and Asymmetric Synthesis of α,ω-Diheterofunctional Reduced Polypropionates via "One-Pot" Zr-Catalyzed Asymmetric Carboalumination-Pd-Catalyzed Cross-Coupling Tandem Process", J. Am. Chem. Soc., 127, 2838-9 (2005).
  2. Huang, Z. et al.: "Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes: ZACA-Lipase-Catalyzed Acetylation Synergy", Adv. Synth. Catal., 349, 539-45 (2007).

Description Wako Cat. No. (Pkg. Size)
(+)-(NMI)2ZrCl2
[(+)-Bis{1-[(1'R, 2'R, 5'S)-2'-isopropyl-5'-methylcyclohexyl]indenyl}zirconium (IV) Dichloride]
022-16111 (200 mg)
028-16113         (1 g)
(-)-(NMI)2ZrCl2
[(-)-Bis{1-[(1'S, 2'S, 5'R)-2'-isopropyl-5'-methylcyclohexyl]indenyl}zirconium (IV) Dichloride]
025-15981 (200 mg)
021-15983         (1 g)
For other products, please visit the Wako Online Catalog www.e-reagent.com
D-1 Maruoka Catalysts <Chiral Phase-Transfer Catalysts (PTC)>
Chiral phase-transfer catalysts, which are optically active spiro ammonium salts with 2 binaphthyl rings that allow for easy molecule designing, were invented by Professor Maruoka of the Kyoto University.
(R, R)-3,4,5-Trifluorophenyl-NAS Bromide shows high catalytic activity and high enantioselectivity in asymmetric alkylation of a-amino acid derivatives1). By using (R, R)-3,5-Bistrifluoromethylpehnyl-NAS Bromide, β-hydroxy α-amino acid derivatives, which are important chiral units of biologically active proteins, are obtained in good yield by the aldol reaction of glycine derivatives with aldehydes. It was found that erythro isomers, which are major products, were obtained with high enantioselectivity2).
[Structural formula]
(R,R)-3,4,5-Trifluorophenyl-NAS Bromide
Maruoka catalyst RR -Trifluorophenyl Br Form
(S,S)-3,4,5-Trifluorophenyl-NAS Bromide
Maruoka catalyst SS -Trifluorophenyl Br Form
(R,R)-3,5-Bistrifluoromethylphenyl-NAS Bromide
Maruoka catalyst RR -Bistrifluoromethylphenyl Br Form
[Reactions]
Asymmetric alkylation of A-amino acid derivative
Asymmetric aldol reaction of B-hydroxy-A-amino acid derivative
Description Grade Wako Cat. No. (Pkg. Size)
(R, R)-3, 4, 5-Trifluorophenyl-NAS Bromide
[Maruoka catalyst RR-Trifluorophenyl Br Form]
for Organic Synthesis 201-15921 (100 mg)
207-15923 (500 mg)
(S, S)-3, 4, 5-Trifluorophenyl-NAS Bromide
[Maruoka catalyst SS-Trifluorophenyl Br Form]
for Organic Synthesis 201-16401 (100 mg)
207-16403 (500 mg)
(R, R)-3, 5-Bistrifluoromethylphenyl-NAS Bromide
[Maruoka catalyst RR-Bistrifluoromethylphenyl Br Form]
for Organic Synthesis 029-14921 (100 mg)
025-14923 (500 mg)
(S, S)-3,5-Bistrifluoromethylphenyl-NAS Bromide
[Maruoka catalyst SS-Bistrifluoromethylphenyl Br Form]
for Organic Synthesis 026-16251 (100 mg)
022-16253 (500 mg)
[References]
  1. T. Ooi, M. Kameda, H. Tannai, K. Maruoka : Tetrahedron Lett., 41, 8339 (2000).
  2. T. Ooi, M. Taniguchi, M. Kameda, K. Maruoka : Angew. Chem. Int. Ed., 41, 4542 (2002).
For other products, please visit the Wako Online Catalog www.e-reagent.com
D-2 Kawabata Acylation Catalyst <Chemo- & Regioselective Acylation>
[Features]
It is a catalyst for selective acylation of the hydroxyl groups at 4-position of glucose derivatives.
Unlike the traditional methods, tedious procedures such as protection/deprotection are not required and diacylation, which is a concern when the enzyme methods are used, does not occur.
This product can be utilized in short-step synthesis of sugar derivatives/glycosides.
Kawabata Acylation Catalyst (1) strictly distinguishes between 4 hydroxyl groups of sugar and induces acylation only at 4-position where the reactivity is originally low. Diacylation does not occur. When the traditional protection-deprotection procedure is used, the same molecular conversion requires 5 steps and results in low yield of 46%. Proposed transition state model for the chemo- & regioselective acylation of octyl -D-gycopyranoside catalyzed by Kawabata Acylation Catalyst Two hydrogen bonds (red) between catalyst molecule and substrate sugar (blue) act effectively.
This figure illustrates that the substrate molecule approaches from the upper side of the catalyst, where the substrate molecules are recognized by the side chain of the 2'-position.
When the substrate molecule approaches from the under side of the catalyst, the side chain of the 5'-position recognizes the substrate. As the catalyst molecule has C2-symmetric resulting in the same transition state by approach of the substrate from both sides, acylation is carried out with high selectivity.
[Reference]
Kawabata, T., Muramatsu, W., Nishio, T., Shibata, T. and Schedel, H.: "A Catalytic One-Step Process for the Chemo-and Regioselective Acylation of Monosaccharides.", J. Am. Chem. Soc., 129, 12890 (2007).
Description Grade Wako Cat. No. (Pkg. Size) Storage
Kawabata Acylation Catalyst
2',5'-[4-(N-Pyrrolidinyl)pyridine]bis[(2-acetylamido)-3-
(1H-indol-3-yl)]propionic Acid Octyl Ester
C49H60N6O6 = 829.04
for Organic Synthesis 119-00781 (50 mg) Keep at 2~10°C
For other products, please visit the Wako Online Catalog www.e-reagent.com
D-3 Catalysts for Alcohol Oxidation <1-Me-AZADO>
Oxidation reaction is traditionally carried out by using chromic acid, hypervalent iodine reagents (IBX oxidation, Dess-Martin oxidation), ruthenium and the like, but these reagents have some safety and operability problems. TEMPO [2, 2, 6, 6-tetramethyl 1-pineridinyloxy] is also known as a nitroxyl-radical oxidative catalyst, but it is known that it cannot oxidize bulky secondary alcohol efficiently and the derived oxoammonium ions degrade under basic conditions.
Wako has launched a stable nitroxyl radical class of catalysts, 2-azaadamantane N-oxyl (AZADO) and 1-Me-AZADO, for highly efficient oxidation of alcohols, which is developed by Iwabuchi at Tohoku University (Japan). AZADO and 1-Me-AZADO exhibit superior catalytic proficiency to TEMPO, converting various sterically hindered alcohols to the corresponding carbonyl compounds in excellent yields1). In addition, the robustness of adamantane skeleton contributes to the improvement of strength and, eventually, durability of the catalyst.
[Features]
  • Superior catalytic proficiency Amount of catalyst: 0.01 mol% (more than 20 times amount of TEMPO)
  • Capable of oxidation of sterically-hindered secondary OH groups
[Chemical Structures]
[Reactions]
■Comparison of catalytic activities between TEMPO and 1-Me-AZADO under Anelli's conditions
■Comparison of catalytic activities between TEMPO and 1-Me-AZADO under Margarita's conditions
[References]
  1. Shibuya, M., Tomizawa, M., Suzuki, I., Iwabuchi, Y.: g2-Azaadamantane N-Oxyl (AZADO) and 1-Me-AZADO: Highly Efficient Organocatalysts for Oxidation of Alcohols", J. AM. Chem. Soc., 128, 8412-8413 (2006)
  2. Iwabuchi, Y.: J. Synth. Org. Chem., Jpn., 66, 1076 (2008).
Description Grade Wako Cat. No. (Pkg. Size) Storage
2-Azaadamantane-N-oxyl
[AZADO]
for Organic Synthesis 014-22001 (100 mg)
010-22003 (500 mg)
018-22004 ( 1 g )
Keep at 2~10°C
1-Methyl-2-azaadamantane-N-oxyl
[1-Me-AZADO]
for Organic Synthesis 132-15261 (100 mg)
138-15263 (500 mg)
Keep at 2~10°C
For other products, please visit the Wako Online Catalog www.e-reagent.com

E-1 Medium Fluorous Mukaiyama Reagent
Organic molecules bearing small fluorous tags such as C8F17 are called light fluorous molecules. Light fluorous reagent, which has fluorine contents in the range of 30-40% of their molecular weight is especially convenient since it typically induces reactions of organic substrates under the same conditions as their non-fluorous counterparts. On the other hand, it is reliably removed from the crude reaction products by fluorous solid phase extraction.

Today, a simple separation of a fluorous pyridone by-product, where fluorous solid phase extraction is not necessary, is possible when a medium weight fluorous version of Mukaiyama reagent bearing a C10F21 fluorous tag, giving it a fluorine content around 49% of its molecular weight is used.

We launched the medium fluorous Mukaiyama reagent. Using this reagent, the by-product is effectively separated as a precipitate by adding water to the reaction mixture after coupling reaction and filtering are complete.
[Features]
Easy to separate and recover by just filtering
■Exaple of Usage ■Reactions
Description Wako Cat. No. (Pkg. Size)
Medium Fluorous Mukaiyama Reagent
2-Chloro-1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosa. uorododecyl)
pyridinium Tri. uoromethanesulfonate
087-09011 (100 mg)
083-09013 (500 mg)
Related Products
Light Fluorous Mukaiyama Reagent
2-Chloro-1-(1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoroundecyl) pyridinium Trifluoromethanesulfonate
036-20101 (200 mg)
032-20103 (1 g)
Wakopak® Fluofix®-ll 120E (for HPLC) 001-00030 (4.6 mm I.D. x 150 mm)
001-00030 (4.6 mm I.D. x 250 mm)
For other products, please visit the Wako Online Catalog www.e-reagent.com
E-2 Fluorinating Agents
Nucleophilic fluorinating agents are widely used in the synthesis of fluorine-containing pharmaceutical intermediates and functional materials.
DAST (Diethylaminosulfur Trifluoride) is a typical nucleophilic fluorinating agent.
With this reagent, alcohol is substituted by fluorine and difluoride is added to ketone and aldehyde.
BAST [Bis (2-methoxyethyl)aminosulfur Trifluoride] is an analogous compound of DAST. It is superior in thermal stability compared to DAST, and is easy to handle.
[Features]
  · Wide range of reactivity
    - Alcohol (hydroxyl group) is substituted by fluorine atom
    - Carbonyl group in aldehyde and ketone is substituted by difluoromethylene group
DAST (Diethylaminosulfur Trifluoride)
■Fluorinating Reactions using DAST
BAST (Bis (2 -methoxyethyl)aminosulfur Trifluoride)
BAST is an analogous compound of DAST. It is superior in thermal stability compared to DAST, and is easy to handle.
[References]
  1. Robins, M. J., et al.: J. Org. Chem., 58, 3800 (1993).
  2. Tellier, F. and Sauvetre, R.: Tetrahedron Lett., 32, 5963 (1991).
  3. Schwesinger, R., et al.: Angew. Chem., 32, 1361 (1994).
  4. Wollenweber, M., et al.: ibid, 33, 117 (1994).
Description Wako Cat. No. (Pkg. Size)
DAST [Diethylaminosulfur Trifluoride] 045-31101 (5 g); 043-31102 (25 g)
BAST [Bis(2 -methoxyethyl)aminosulfur Trifluoride] 023-15801 (5 g); 021-15802 (25 g)
For other products, please visit the Wako Online Catalog www.e-reagent.com


F-1 Cyclic Triolborates
Suzuki-Miyaura coupling reaction is carried out typically in the presence of a base and often in the coexistence of water as many boronic acids convert to cyclic anhydrides by dehydrotrimerization. However, since some boronic acids are hydrolyzed in basic aqueous solution, a large excess of boronic acids are often required.
Organic cyclic-triolborate salts are the ate complexed borate reagents developed by Miyaura, et al. There is no need to add bases in cross coupling reactions catalyzed by palladium. They may be used in aqueous and nonaqueous systems. They are also useful in N-arylation reaction with copper catalysts.
■Coupling Reactions using various triolborates ■Biaryl Coupling Reactions with Triolborate
■Coupling Reaction with 2-Pyridine Triolborate
[Reference]
Yamamoto Y., Takizawa M., Yu X. and Miyaura N.: "Cyclic Triolborates:Air- and Water-Stable Ate Complexes of Organoboronic Acids", Angew.Chem. Int. Ed., 47, 928-931 (2008).
Product List of Cyclic Triolborate (excerpted)
Besides above products, Wako provides over 30 kinds of cyclic triolborates.
Search the website www.e-reagent.com using "triolborate" as a keyword.
Please feel free to contact us if you want to order other package sizes.

 Listed products are intended for laboratory research use only, but not to be used for drug, food or human use.
 Please visit our online catalog to search for other products from Wako ; www.e-reagent.com
 This brochure may contain products that cannot be exported to your country due to regulations.
 Bulk quote requests for some products are welcomed. Please contact us.

Wako Pure Chemical Industries, Ltd.
www.wako-chem.co.jp
1-2, Doshomachi 3-Chome
Chuo-Ku, Osaka 540-8605, Japan
Tel: 81-6-6203-3741
Fax: 81-6-6201-5964
Online Catalog: www.e-reagent.com
Wako Chemicals USA, Inc.
www.wakousa. com
Toll-Free (U.S. only): 1-877-714-1920
Head Office (Richmond, VA):
Tel: 1-804-714-1920/ Fax: 1-804-271-7791
Los Angeles Sales Office (Irvine, CA):
Tel: 1-949-679-1700 / Fax: 1-949-679-1701
Boston Sales Office (Cambride, MA):
Tel: 1-617-354-6772 / Fax: 1-617-354-6774
Wako Chemicals GmbH
www.wako-chemicals.de
European Office:
NissanstraBe 2, D-41468
Neuss, Germany
Tel: 49-2131-311-0
Fax: 49-2131-311100