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Apeiron Synthesis has developed a growing portfolio of over twenty exceptional metathesis catalysts designed to accommodate a wide range of applications, with catalyst availability from gram to multi-kilogram quantities, suitable for applications in R&D as well as in large scale production. Our technology platform offers customers:• Broad and growing portfolio of catalysts with applications to all metathesis reaction types• Catalysts optimized for continuous flow - with high turnover and extended reusability• High efficiency catalysts for metathesis in water, at room temperature and on solid support• Extensive metathesis centered know-how, unique tools and process chemistry expertise that combine to meet challenging
chemistry objectives• A variety systems of catalyst-activator and catalyst-retardant applicable in metathesis polymerization reactions
Apeiron Synthesis is dedicated to providing products and services that transform our customers’ chemistry to save time and money with cost effective, efficient, sustainable processes.money with cost effective, efficient, sustainable processes.
Our technology platform is highly modular, enabling us to manufacture catalysts incorporating process-specific structural modi-fications in the labile (ionic and benzylidene) and non-labile (NHC and CAAC) ligands. Apeiron takes advantage of proprietary technology that is the result of our in-house research program as well as intellectual property licensed from leading European industrial and academic partners.
We specialize in modifications of the NHC and CAAC ligand to append customized utility tags - affording novel catalyst traits for process-specific requirements, such as altered solubility profiles, simpler post-reaction work-up or easier removal of ruthenium residues from products.
Apeiron catalysts have been extensively tested and some have also become industry standards. When compared to other op-tions, our catalysts have demonstrated clear superiority with respect to reaction time, temperature, dilution factor, reactivity and selectivity.
Apeiron’s catalyst offerings
The Apeiron Advantage
How does it work?
Validation by Industry
Transforming your chemistr y
Apeiron’s olefinmetathesis catalysts
Apeiron Synthesis / © 2018
References:
Group characteristics and application:
• Has proven efficiency in macrocycylization• High initiation rate, even below room temperatures• Excellent selectivity
Other catalysts in this group:
V. Farina, C. Shu, X. Zeng, X. Wei, Z. Han, N. K. Yee, C. H. Senanayake; Second-Generation Process for the HCV Protease Inhibi-tor BILN 2061: A Greener Approach to Ru-Catalyzed Ring-Closing Metathesis; Organic Process Research & Development, 13, 250–254 (2009)
Nitro-Grela Catalyst Group
Core Catalyst: nitro-GrelaAS2032CAS: 502964-52-5PCT/EP2003/011222
RuCl
ClO
NN
NO2
OPNB
O
NBOCO
NH
O
O
N
OPNB
O
NBOCO
NH
O
O
N
(0.1 mol %)OCH3
O O
OCH3toluene, 0.2M 110 oC, 30 min
93%
nitro-Grela
AS2033
AS2053
AS2051
AS2080
AS2052
AS2033 AS2051 AS2052
AS2053 AS2080
RuCl
ClO
NN
NO2
RuCl
ClO
NN
NO2
RuI
IO
NN
NO2
RuI
IO
NN
NO2
RuCl
ClO
PCy3
NO2
AS2033 AS2051 AS2052
AS2053 AS2080
RuCl
ClO
NN
NO2
RuCl
ClO
NN
NO2
RuI
IO
NN
NO2
RuI
IO
NN
NO2
RuCl
ClO
PCy3
NO2
AS2033 AS2051 AS2052
AS2053 AS2080
RuCl
ClO
NN
NO2
RuCl
ClO
NN
NO2
RuI
IO
NN
NO2
RuI
IO
NN
NO2
RuCl
ClO
PCy3
NO2
AS2033 AS2051 AS2052
AS2053 AS2080
RuCl
ClO
NN
NO2
RuCl
ClO
NN
NO2
RuI
IO
NN
NO2
RuI
IO
NN
NO2
RuCl
ClO
PCy3
NO2
AS2033 AS2051 AS2052
AS2053 AS2080
RuCl
ClO
NN
NO2
RuCl
ClO
NN
NO2
RuI
IO
NN
NO2
RuI
IO
NN
NO2
RuCl
ClO
PCy3
NO2
Apeiron Synthesis / © 2018
Apeiron Synthesis / © 2018
Bis-CAAC catalyst group
References:
Group characteristics and application:
• High stability• Excellent for CM of terminal olefins, ethenolysis• Very good for mRCM and RCM leading to small/medium rings
Group characteristics and application:
• Excellent for ring opening metathesis polymerization of highly reactive monomers
• Highly tunable activity with co-catalysts and additives for specific polymerization process requirement
• Long shelf life of ready-to-use formulations• Compatible with wider range of fibers and mineral fillers
Core Catalyst: UltraCat
Other catalysts in this group:
R. Gawin, A. Kozakiewicz, P. A. Guńka, P. Dąbrowski, K. Skowerski, „Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Effi cient Tool for Olefin Metathesis”, Angew. Chem. Int. Ed., 56, 910, (2017)
AS2086CAS: 2055540-61-7PCT/IB2016/054486
Ultra LatMetAS2098
RuCl
Cl
Ph
N
NPh
Ph
RuCl
Cl
Ph
N
N
AS2098
CO2Me7
7
UltraCat (3ppm)
ethylene 10 barneat, 50oC
NO GLOVEBOXmethyl oleate92% purity
(commercially available)
7
CO2Me7
TON = 88 000Selectivity 95%
References:
Group characteristics and application:
• High stability• Excellent for macrocyclic RCM• Excellent for CM with nitriles• Very good in CM of terminal olefins
Other catalysts in this group:
R. Gawin, A. Tracz, M. Chwalba, A. Kozakiewicz, B. Trzaskowski, K. Skowerski, “Cyclic Alkyl Amino Ruthenium Complexes-Efficient Catalysts for Macrocyclization and Acrylonitrile Cross Metathesis”, ACS Catalysis, 7 (8), 5443–5449 (2017).
Nitro-CAAC catalyst group
Core Catalyst: UltraNitroCatAS2091CAS: 2106819-64-9PCT/IB2016/054486
AS2101 AS2095 AS2100 AS2099
AS2092 AS2096
CO2Me7
CN
UltraNitroCat(15 ppm)
Toluene, 85oC
CO2Me7CN
+
Conversion 75%Selectivity 75%TON = 38 000
RuCl
ClO
N
NO2
Ph
RuCl
ClO
N
NO2
RuCl
ClO
N
NO2
RuCl
ClO
N
NO2
RuI
IO
N
NO2
RuI
IO
N
NO2
Ph
AS2101 AS2095 AS2100 AS2099
AS2096AS2092
RuCl
ClO
N
NO2
Ph
RuCl
ClO
N
NO2
RuCl
ClO
N
NO2
RuCl
ClO
N
NO2
RuI
IO
N
NO2
RuI
IO
N
NO2
Ph
AS2101 AS2095 AS2100 AS2099
AS2096AS2092
RuCl
ClO
N
NO2
Ph
Apeiron Synthesis / © 2018
Latent Catalyst Group
References:
Chemically and thermally activated
Thermally activated
Group characteristics and application:
• Latent in the presence of reactive monomers• High activity and efficiency after activation• Chemical and/or thermal activation required
Core Catalyst: LatMet
Other catalysts in this group:
A. Kozłowska, M. Dranka, M. Zachara, E. Pump, C. Slugovc, K. Skowerski, K. Grela; Chelating Ruthenium Phenolate Complexes—Synthesis, General Catalytic Activity and Applications in Olefin Metathesis Polymerization; Chem. Eur. J., 20(43), 14120 – 14125 (2014)
AS2035CAS: 1407229-58-6PCT/EP2013/065839
LatMet (50 ppm)28 oC, 4 h
NO CONVERSION
HCl, 60 oC10 min
>99%
RuCl
ClN
NN
O
ORu
Cl
ClN
NN
O
O RuCl
ClN
NN
O
O
AS2036
AS2056
AS2037
AS2055 AS2070
RuO
Cl
NN
Cy3P
RuO
Cl
Cy3P
NN
NO2
AS2036
RuO
Cl
Cy3P
NN
AS2037
RuO
Cl
Cy3P
NN
NO2
AS2036
RuO
Cl
Cy3P
NN
AS2037
Apeiron Synthesis / © 2018
References:
Group characteristics and application:
• Low residual ruthenium in the product after implementation of simple purification protocols
• Allows for catalyst recovery and reuse• Excellent compatibility with ACS-grade green solvents (esters,
ethers, hydrocarbons)
Other catalysts in this group:
K. Skowerski, P. Kasprzycki, M. Bieniek, T. K. Olszewski; Efficient, durable and reusable olefin metathesis catalysts with high affinity to silica gel; Tetrahedron 69, 7408 – 7415 (2013)
GreenCat Catalyst Group
Core Catalyst: GreenCatAS2034CAS: 1448663-06-6PCT/EP2013/062435
RuCl
ClO
NN
O
NO
GreenCat (0.1 mol%)
40 oC, 1.5 h
non-degassed, non-dryied ACS grade AcOEt
NBoc
O
NNBoc
O
N
92%
MeOOC8
O
O+GreenCat (0.5 mol%)
40 oC, 1.5 hMeOOC
8O
O
non-degassed, non-dryied ACS grade i-PrOH
88%, E/Z 9/1
AS2094
non-degassed, non-dried ACS grade AcOEt
non-degassed, non-dried
AS2094
RuI
IO
NN
O
NO
Apeiron Synthesis / © 2018
AS2041 AS2054 AS2066 AS2038
RuCl
ClO
NN
N
NCl
RuCl
ClO
NN
ClN
NO2
RuCl
ClO
NN
N
NBF4
AS2049
RuCl
ClO
NN
N
NPF6
AS2050
RuCl
ClO
NN
PF6N
RuCl
ClO
NN
N
NCl
AS2061
RuCl
ClO
NN
BF4N
RuCl
ClO
NN
N
NPF6
AS2083
AS2041 AS2054 AS2066 AS2038
RuCl
ClO
NN
N
NCl
RuCl
ClO
NN
ClN
NO2
RuCl
ClO
NN
N
NBF4
AS2049
RuCl
ClO
NN
N
NPF6
AS2050
RuCl
ClO
NN
PF6N
RuCl
ClO
NN
N
NCl
AS2061
RuCl
ClO
NN
BF4N
RuCl
ClO
NN
N
NPF6
AS2083
Ammonium-Tagged Catalyst Group
References:
Group characteristics and application:
• Simple removal of residual ruthenium by extraction with water or work-up with silica gel
• Residual ruthenium < 5 ppm• High activity in the temperature range of 40 – 110° C• Designed to be deposited on solid support to increase reusability
or for continuous flow applications• Good solubility in neat water (up to 60 mg/ml)• High stability in non-degassed water
only 1.6 ppmof residual ruthenium
1 mol%of StickyCat Cl
Core Catalyst: StickyCat Cl
Other catalysts in this group:
K. Skowerski, C. Wierzbicka, G. Szczepaniak, Ł. Gułajaski, M. Bieniek, K. Grela; Easily removable olefin metathesis catalysts; Green Chem., 14(12), 3264 – 3268, (2012)
AS2040CAS: 1452227-72-3PCT/EP2013/053967
RuCl
ClO
NN
ClN
O
O10 000 ppm
of StickyCat Cl
DCM, 40oC 80 min 97%
+TBSO TBSO
O
O
only 1.6 ppmof residual ruthenium
AS2041
AS2049
AS2054
AS2050
AS2066
AS2061
AS2038
AS2063
Apeiron Synthesis / © 2018
North AmericaApeiron Synthesis, Inc Cambridge Innovation Center, 1 Broadway , Cambridge, MA 02142 USA
Grazyna Szymanska, PhDGlobal Business [email protected]: (+1) 781-608-5859
EuropeApeiron Synthesis S.A. Wroclaw Technology Parkul. Duńska 9, 54-427 WrocławPoland
Joanna DrygajłoSales Manager and Technical Support [email protected].: (+48) 668-191-409
AvailabilityAll our Core Catalysts are available from STREM, TCI, Sigma Aldrich for R&D purposes.
Products available directly from Apeiron Synthesis: Extended Core Catalysts (Ammonium-Tagged Catalysts Group, GreenCat Catalysts Group, Latent Catalysts Group, nitro-Grela Catalysts Group and CAAC Catalysts Group) Het-erogeneous Catalysts - provided on different solid support – on demand Process-Specific Catalysts - individually synthesized catalysts for both R&D and Process Chemistry with no restrictions on quantity
To place an order or for technical information please contact:
www.apeiron-synthesis.com
Technical support
• General help: [email protected]• Ordering mail: [email protected]
Apeiron Synthesis / © 2018
