301224-40-8

Usage

Uses

Used in Pharmaceutical Industry:
(1,3-BIS-(2,4,6-TRIMETHYLPHENYL)-2-IMIDAZOLIDINYLIDENE)DICHLORO(O-ISOPROPOXYPHENYLMETHYLENE)RUTHENIUM is used as a catalyst for various metathesis reactions in the pharmaceutical industry. Its ability to initiate reactions at lower temperatures and efficiently handle electron-deficient substrates, such as fluorinated olefins, makes it a preferred choice for large-scale applications.
Used in Olefin Cross-Metathesis with Fluorinated Olefins (CM):
In the field of organic chemistry, this ruthenium complex is used as a catalyst for olefin cross-metathesis with fluorinated olefins. Its efficiency in this application allows for the formation of new chemical bonds and the synthesis of complex molecules, which are crucial in the development of pharmaceutical compounds.
Used in Ring-Closing Metathesis (RCM):
(1,3-BIS-(2,4,6-TRIMETHYLPHENYL)-2-IMIDAZOLIDINYLIDENE)DICHLORO(O-ISOPROPOXYPHENYLMETHYLENE)RUTHENIUM is utilized as a catalyst in ring-closing metathesis reactions. This process involves the formation of cyclic compounds from acyclic precursors, which is an essential step in the synthesis of various pharmaceutical and chemical products.
Used in Ring-Opening Metathesis (ROM):
This ruthenium complex is also employed as a catalyst in ring-opening metathesis reactions. It facilitates the conversion of cyclic compounds into their acyclic counterparts, which is vital for the synthesis of linear polymers and other chemical products.
Used in a Sequence of a Metathesis Reaction and Subsequent Dihydroxylation of the Newly Formed Double Bond:
(1,3-BIS-(2,4,6-TRIMETHYLPHENYL)-2-IMIDAZOLIDINYLIDENE)DICHLORO(O-ISOPROPOXYPHENYLMETHYLENE)RUTHENIUM is used in a sequence of metathesis reactions followed by the dihydroxylation of the newly formed double bond. This application allows for the creation of complex molecular structures with specific functional groups, which are essential in the development of new pharmaceutical compounds and materials.

InChI:InChI=1/C21H26N2.C10H12O.2ClH.Ru/c1-14-9-16(3)20(17(4)10-14)22-7-8-23(13-22)21-18(5)11-15(2)12-19(21)6;1-8(2)11-10-7-5-4-6-9(10)3;;;/h9-12H,7-8H2,1-6H3;3-8H,1-2H3;2*1H;/q;;;;+2/p-2/rC31H38Cl2N2ORu/c1-20(2)36-28-12-10-9-11-27(28)19-37(32,33)31-34(29-23(5)15-21(3)16-24(29)6)13-14-35(31)30-25(7)17-22(4)18-26(30)8/h9-12,15-20H,13-14H2,1-8H3

Upstream product

• 203714-71-0 Hoveyda-Grubbs catalyst first generation 
• 246047-72-3 dichloro(tricyclohexylphosphino)(benzylidene)(1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)ruthenium(III) 
• 67191-35-9 o-isopropoxystyrene 
• 7647-01-0 hydrogenchloride 
• 533934-20-2 1-isopropoxy-2-(prop-1-en-1-yl)benzene 
• 246047-72-3 tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride 
• 100-42-5 styrene 

Relevant academic research and scientific papers

Latent ruthenium olefin metathesis catalysts featuring a phosphine or an N-heterocyclic carbene ligand

The synthesis and characterization of latent 18-electron ruthenium benzylidene complexes (PCy3)((κN,O)-picolinate)2RuCHPh (5) and (H2IMes)((κN,O)-picolinate)2RuCHPh (6) are described. Both complexes appear as two isomers. The ratio between the isomers is dependent on l-type ligand. The complexes are inactive in ring-closing metathesis and ring-opening metathesis polymerization reactions even at elevated temperatures in the absence of stimuli. Upon addition of HCl, complexes 5 and 6 become highly active in olefin metathesis reactions. The advantage of the latent catalysts is demonstrated in the ring-opening metathesis polymerization of dicyclopentadiene, where the latency of 6 assures adequate mixing of catalyst and monomer before initiation. Trapping experiments suggests that the acid converts the 18-electron complexes into their corresponding highly olefin metathesis active 14-electron benzylidenes.

Ionically tagged ru-alkylidenes for metathesis reactions under biphasic liquid-liquid conditions

The synthesis of the novel ionic Ru-alkylidenes [Ru[(4-CO2)(1-CH3)Py+)]2(IMesH2)(=CH-2-(2-PrO)-C6H4)][OTf-]2 (1, IMesH2=1,3-dimesitylimidazolin-2

A practical larger scale preparation of second-generation hoveyda-type catalysts

A two-step synthesis of the nitro-substituted Hoveyda-Grubbs olefin metathesis catalyst 4b from the parent first-generation Hoveyda-Grubbs complex 3a has been developed. The second-generation ruthenium catalyst was prepared by mixing together all ingredients, including a NHC ligand precursor and a strong base in an appropriate solvent. The formation of desired product 3b was separated from the liberated phosphine and decomposition products by flash chromatography using CH2Cl2 as the eluent. A good chelating 2-isopropoxybenzylidene fragment in 3b was replaced with the less chelating 5-nitro-2-isopropoxybenzylidene ligand. The resulting mixture was separated by crystallization from EtOAc from CH2Cl2 and finally from methanol. The method does not require extensive use of silica gel chromatography and can be easily scaled up.

Insertion of imines into vinylcyclopropanes catalyzed by nucleophilic iron complexes: A formal [3+2]-cycloaddition strategy for the synthesis of substituted pyrrolidine derivatives

Pyrrols are substructures in various biological active molecules. A straightforward iron-catalyzed synthesis of pyrrols via insertion of an imine into a vinylcyclopropane is presented. The corresponding pyrrols are obtained in moderate to good yields. Scope and limitations will be discussed.

Reactivity and selectivity differences between catecholate and catechothiolate ru complexes. Implications regarding design of stereoselective olefin metathesis catalysts

The origins of the unexpected finding that Ru catechothiolate complexes, in contrast to catecholate derivatives, promote exceptional Z-selective olefin metathesis reactions are elucidated. We show that species containing a catechothiolate ligand, unlike catecholates, preserve their structural integrity under commonly used reaction conditions. DFT calculations indicate that, whereas alkene coordination is the stereochemistry-determining step with catecholate complexes, it is through the metallacyclobutane formation that the identity of the major isomer is determined with catechothiolate systems. The present findings suggest that previous models for Z selectivity, largely based on steric differences, should be altered to incorporate electronic factors as well.

Versatile Ru-based metathesis catalysts designed for both homogeneous and heterogeneous processes

The synthesis of new ruthenium-based catalysts applicable for both homogeneous and heterogeneous metathesis is described. Starting from the Hoveyda-Grubbs first generation (1) and the Hoveyda-Grubbs second generation (2) catalysts the homogeneous catalysts [RuCl((RO)3Si-C3H6-N(R′)-CO-C3F6-COO)({double bond, long}CH-o-O-iPr-C6H4)(SIMes)] (4: R = Et, R′ = H; 5: R = R′ = Me) (SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) were prepared by substitution of one chloride ligand with trialkoxysilyl functionalized silver carboxylates (RO)3Si-C3H6-N(R′)-CO-C3F6-COOAg (3a: R = Et, R′ = H; 3b: R = R′ = Me). These homogeneous ruthenium-species are among a few known examples with mixed anionic ligands. Exchange of both chloride ligands afforded the catalysts [Ru((RO)3Si-C3H6-N(R′)-CO-C3F6-COO)({double bond, long}CH-o-O-iPr-C6H4)(SIMes)] (9: R = Et, R′ = H; 11: R = R′ = Me) and [Ru((RO)3Si-C3H6-N(R′)-CO-C3F6-COO)({double bond, long}CH-o-O-iPr-C6H4)(PCy3)] (8: R = Et, R′ = H; 10: R = R′ = Me). The reactivity of the new complexes was tested in homogeneous ring-closing metathesis (RCM) of N,N-diallyl-p-toluenesulfonamide and TONs of up to 5000 were achieved. Heterogeneous catalysts were obtained by reaction of 4, 5 and 8-11 with silica gel (SG-60). The resultant supported catalysts 4a, 5a, 8a-11a showed reduced activity compared to their homogenous analogues, but rival the activity of similar heterogeneous systems.

High-Yield Synthesis of a Long-Sought, Labile Ru-NHC Complex and Its Application to the Concise Synthesis of Second-Generation Olefin Metathesis Catalysts

The controlled reaction of [RuCl2(p-cymene)]2 with H2IMes generates the previously challenging precatalyst and Ru synthon RuCl2(p-cymene)(H2IMes) (Ru-2) in 96% isolated yield. Critical to success is inhibiting premature p-cymene displacement. This is achieved by carrying out the synthesis at ambient temperatures, protected from light, and at sufficient dilutions (25 mM in THF) to enable stoichiometric control and inhibit bimolecular decomposition. The ease with which p-cymene loss can be deliberately induced, however, is key to the utility of Ru-2 in both catalysis and catalyst synthesis. The transformation of Ru-2 into two second-generation olefin metathesis catalysts is described. RuCl2(H2IMes)(=CH(o-C6H4-OiPr)) (HII) and RuCl2(H2IMes)(PPh3)(=CHPh) GII′ (a desirable, faster-initiating analogue of GII) are accessible in ca. 80% yield over two steps from commercially available [RuCl2(p-cymene)]2. Synthesis from RuCl2(PPh3)3, in comparison, requires three or four steps for HII or GII′, respectively, and proceeds in lower yields.

Ruthenium Olefin Metathesis Catalysts Featuring a Labile Carbodicarbene Ligand

Ruthenium benzylidene complexes containing a carbodicarbene (CDC) ligand are reported. Mechanistic studies indicate that the CDC ligand can dissociate under relatively mild conditions to afford active olefin metathesis catalysts. These catalysts were found to be effective at ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions.

Light-Driven gem Hydrogenation: An Orthogonal Entry into “Second-Generation” Ruthenium Carbene Catalysts for Olefin Metathesis

The newly discovered light-driven gem hydrogenation of alkynes opens an unconventional yet efficient entry into five-coordinate Grubbs-type ruthenium carbene complexes with cis-disposed chloride ligands. Representatives of this class featuring a chelate substructure formed by an iodo-substituted benzylidene unit react with (substituted) 2-isopropoxystyrene to give prototypical “second-generation” Grubbs-Hoveyda complexes for olefin metathesis. The new approach to this venerable catalyst family is safe and versatile as it uses a triple bond rather than phenyldiazomethane as the ultimate carbene source and does not require any sacrificial phosphines.

Activation of olefin metathesis complexes containing unsymmetrical unsaturated N-heterocyclic carbenes by copper and gold transmetalation

The activation of ruthenium-indenylidene complexes containing two unsymmetrical unsaturated N-heterocyclic carbenes (u2-NHCs) by a transmetalation process is reported. The use of copper(i) or gold(i) chlorides promotes the rapid trapping of one NHC ligand, which releases the catalytically active Ru-species. Impressive initiation rates with full-conversions are observed within one minute. This practical protocol demonstrates excellent catalytic performances in various ring-closing metathesis (RCM) and self-metathesis (SM) reactions.