WO2005030782A2 - Ligands carbene et leur utilisation - Google Patents

Ligands carbene et leur utilisation Download PDF

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WO2005030782A2
WO2005030782A2 PCT/CA2004/001781 CA2004001781W WO2005030782A2 WO 2005030782 A2 WO2005030782 A2 WO 2005030782A2 CA 2004001781 W CA2004001781 W CA 2004001781W WO 2005030782 A2 WO2005030782 A2 WO 2005030782A2
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compound
group
complex
formula
catalyst
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WO2005030782A3 (fr
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Darrin S. Richeson
Patrick R. Bazinet
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University Of Ottawa
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds

Definitions

  • the present invention relates to the field of carbene compounds, and in particular carbene compounds that are suitable for use as ligands in connection with transition metal centres.
  • the ylidenes A and B represent the typical architectures of stable nucleophilic singlet carbenes. These species have been largely restricted to five-membered heterocyclic rings and the more stable unsaturated species (A) possess the 6 ⁇ electron structure expected for aromatic systems. ' ' Particular examples of catalysts and reactions that have successfully employed carbenes of type A and B are Grubb's "second generation" olefin metathesis catalysts, which typically involve coordination of a Ru atom.
  • Group VIII transition metal olefin metathesis catalysts, specifically ruthenium and osmium alkylidene complexes, have been described in U.S. Pat. Nos. 5,312,940 and 5,342,909, which are incorporated herein by reference.
  • the ruthenium and osmium alkylidene complexes disclosed in these patents and applications are of the general formula I:
  • M is ruthenium or osmium
  • X and X 1 are anionic ligands
  • L and L 1 are neutral electron donors.
  • U.S. Pat. Nos. 5,312,940 and 5,342,909 disclose specific vinyl alkylidene ruthenium and osmium complexes and their use in catalyzing the ring opening metathesis polymerization ("ROMP") of strained olefins.
  • R 1 is hydrogen and R is either a substituted or unsubstituted vinyl group.
  • transition metal based catalysts have been developed, which include modifications to the anionic and neutral ligands (see for example the teachings of US patents 5,959,170, 6,111,121, 6,121,473, and 6,346,652, which are incorporated herein by reference, and references cited therein).
  • modifications to the anionic and neutral ligands see for example the teachings of US patents 5,959,170, 6,111,121, 6,121,473, and 6,346,652, which are incorporated herein by reference, and references cited therein.
  • Some novel carbenes include N-heterocyclic carbenes, which have become universal ligands in organometallic and inorganic coordination chemistry 8 .
  • transitional metal based catalysts comprise expensive transition metals.
  • catalysts for olefin metathesis reactions including, but not limited to, ring-opening metathesis polymerization, ring closing metathesis, cross-metathesis reactions (for example involving at least one acyclic or unstrained cyclic olefin), depolymerization of olefin polymers, C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation, atom transfer radical polymerization (ATRP), and other synthetic synthesis steps that typically involve transition metal catalysts.
  • ring-opening metathesis polymerization for example involving at least one acyclic or unstrained cyclic olefin
  • cross-metathesis reactions for example involving at least one acyclic or unstrained cyclic olefin
  • depolymerization of olefin polymers C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation
  • ATRP atom transfer radical polymer
  • the inventors of the present invention have undertaken the design and development of new stable carbene compounds possessing different scaffolds and electronic structures to those of the prior art.
  • the carbene compounds of the present invention most preferably comprise a perimidine core. This approach places the carbene centre in a six-membered ring, which has significant implications on the steric impact of N substituents of the carbene ring, and appears to leave the divalent carbon as part of a formally seven ⁇ -electron, six-membered heterocyclic ring.
  • the carbene compounds of the present invention exhibit increased steric impact and electron donating ability. These properties manifest themselves by yielding sterically encumbered metal-carbene complexes.
  • the novel electronic framework gives rise to a nucleophilic carbene centre capable of acting as a strong ⁇ - donor ligand.
  • These features enable perimidine-based carbenes of the present invention to provide steric protection and electronic activation to coordinatively unsaturated metal complexes that are vital intermediates in a myriad of catalytic transformations.
  • the carbene compounds of the present invention may be used in conjunction with a broad range of transition metals to develop a new class of transition metal catalysts.
  • a perimidine compound comprising a carbene in the 2 position.
  • the compound has a formula II:
  • R and R 1 are independently selected from the group consisting of: of hydrogen, C 2 - C 20 alkenyl, C 2 -C 20 alkynyl, C ⁇ -C 20 alkyl (including primary, secondary, tertiary, and cyclo alkyls), aromatic, aryl, heterocyclic, C ⁇ -C 0 carboxylate, alkoxy, C 2 -C 20 alkenyloxy, aryloxy, C 2 -C2 0 alkoxycarbonyl, C ⁇ -C 20 alkylthio, C!-C 2 o alkylsulfonyl, C ⁇ -C 20 alkylsulfmyl, silyl or benzyl; each optionally substituted with an aromatic group, C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl group optionally substituted with halogen, Cj-C 5 alkyl, C ⁇ -C 5 alkoxy, or an aromatic group; and
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from the group consisting of hydrogen, halogen, C ⁇ -C 20 alkyl (including primary, secondary, tertiary, and cyclo alkyls), benzyl, silyl, or C ⁇ -C 20 alkoxy, or any two of R 2 , R 3 , R 4 , R 5 , R 6 , or R 7 may be linked together form a C 5 -C 7 carbon ring that is optionally substituted by halogen, Cp C 5 alkyl, or C ⁇ -C 5 alkoxy.
  • R 2 to R are hydrogen.
  • the compound has a structure selected from the group consisting of:
  • a transition metal ligand consisting essentially of a compound according to the present invention.
  • a multidentate transition metal ligand comprising two or more compounds according to the present invention, and one or more linking moieties to covalently link the compounds together.
  • the linking moieties are selected from the group consisting of C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C ⁇ -C 20 alkyl (including primary, secondary, tertiary, and cyclo alkyls), aromatic, aryl, and heterocyclic groups.
  • the multidentate ligand according to the invention has the following structure:
  • R and R are as defined previously, or is a compound selected from the group consisting of:
  • the present invention provides a complex comprising a transition metal atom coordinated by the compound according to the invention, or the ligand according to the invention.
  • the transition metal atom is selected from the group consisting of Al, Zr, Ti, Rh, Pd, Ni, Ru, Pt, Cr, Ir, Fe and Cu. More preferably, the transition metal atom is selected from the group consisting of Rh, Pd, and Ni.
  • the present invention provides a catalyst wherein the catalyst is a complex of the present invention.
  • the catalyst is suitable for use in catalysis of a reaction selected from olefin metathesis, C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation, and atom transfer radical polymerization (ATRP).
  • a reaction selected from olefin metathesis, C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation, and atom transfer radical polymerization (ATRP).
  • the catalyst exhibits a capacity for catalysis of stereospecific C-C bond formation.
  • the catalyst comprises an asymmetric or multidentate carbene ligand. More preferably, the catalyst is capable of catalyzing a cross-coupling or intramolecular coupling reaction.
  • the catalyst has a structure selected from:
  • R, R', R", R'" are selected independently from the group of R and R 1 as previously defined. More preferably, R, R', R" and R'" are isopropyl.
  • the complex of the invention has the following structure:
  • M is selected from Zr or Ti
  • X is halogen or TsO
  • R, R', R" and R'" are selected independently from the group of R and R 1 as defined previously. More preferably R, R', R" and R'" are/?-CH 2 (C 6 H 4 )CH 3 or R and R' are isopropyl and R" and R'" are 2-methylpyridyl.
  • the complex of the invention has the following structure:
  • X is halogen or TsO
  • M is Al
  • R is selected independently from the group of R and R 1 as defined previously. More preferably, X is TsO and R is isopropyl.
  • the complex of the invention has the following structure:
  • M is a Group VIII transition metal
  • Y, Y' and Y" are either CO or halogen
  • R and R' are selected independently from the group of R and R 1 defined previously.
  • the invention provides for a method for the preparation of a compound of the present invention, the method comprising the steps of:
  • R -R are as defined previously;
  • the invention provides for a method for the preparation of a compound of the present invention, the method comprising the steps of:
  • R ,2 -R are as defined previously;
  • the invention provides for a ligand for use in connection with a transition metal catalyst, wherein the ligand comprises a compound according to the present invention.
  • the ligand produces a catalyst, wherein the transition metal catalyst is suitable for use in catalysis of olefin metathesis reactions.
  • the invention provides for a transition metal complex comprising the ligand of the present invention.
  • the invention provides for a use of the transitional metal complex of the invention as a catalyst.
  • the invention provides for a perimidinium salt of the compound of the invention.
  • the invention provides for a method for the preparation of a complex of the invention, the method comprising the step of: reacting a perimidinium salt of formula V
  • R and R 1 to R 7 are as defined previously;
  • M is a group IV transition metal or group XIII metal and p is 3 or 4; and to generate a complex of formula X
  • Z is a compound of formula II
  • s is 1 or 2;
  • X is a counter ion of the perimidinium salt of formula V.
  • Figure 1 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for carbene 3 (hydrogen atoms have been omitted for clarity).
  • Figure 2 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for the carbene complex, (COD)RhCl[C(N 1 Pr) 2 C ⁇ 0 H 6 ], 5 (hydrogen atoms have been omitted for clarity).
  • Figure 3 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for [ , '-di(l-'Pr perimidinium) ort/zo-xylene]dibromide (hydrogen atoms have been omitted for clarity).
  • Figure 4 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for 1,3-diisopropylperimidinium formate (hydrogen atoms have been omitted for clarity).
  • Figure 5 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for l,3-di(cycloheptyl)perimidinium chloride (hydrogen atoms have been omitted for clarity).
  • Figure 6 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme for 1- isopropyl -3-(2-methylpyridy ⁇ ) perimidinium Tosylate (hydrogen atoms have been omitted for clarity).
  • Figure 7 provides a thermal ellipsoid plot showing the molecular structure and atom numbering scheme a selected Pd complex of the invention (hydrogen atoms have been omitted for clarity).
  • carbene In the context of the present specification, the term carbene refers to compounds, ligands or groups comprising one, two or more carbene moieties. The term carbene therefore encompasses dicarbene etc.
  • the present invention provides for perimidine compounds comprising carbene in the 2 position, as well as their precursors, and methods for their production. At least in preferred embodiments, the invention encompasses compounds of the formula II:
  • R and R 1 are independently selected from the group consisting of: of hydrogen, C 2 - C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl (including primary, secondary, tertiary, and cyclo alkyls), aromatic, aryl, C 1 -C20 carboxylate, C ⁇ -C 20 alkoxy, C 2 -C 20 alkenyloxy, aryloxy, C2-C 20 alkoxycarbonyl, C ⁇ -C 2 c alkylthio, C1-C20 alkylsulfonyl, C ⁇ -C2 0 alkylsulfinyl, silyl or benzyl; each optionally substituted with an aromatic group Ci- C 5 alkyl, halogen, -Cs alkoxy, or with a phenyl group optionally substituted with halogen, C ⁇ -C 5 alkyl, d-C 5 alkoxy, or an aromatic group; and
  • R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independently selected from the group consisting of hydrogen, halogen, C 1 -C 20 alkyl (including primary, secondary, tertiary, and cyclo alkyls), benzyl, silyl, or -C 20 alkoxy, or any two of R 2 , R 3 , R 4 , R 5 , R 6 , or R 7 may be linked together form a C 5 -C carbon ring that is optionally substituted by halogen, Ci- C 5 alkyl, or C1-C5 alkoxy.
  • the present invention is not limited to the compounds of formula II, and in fact pertains to all compounds that comprise a perimidine core together with nearby carbene.
  • the invention further encompasses the use of compounds of the present invention as ligands for transition metal complexes and catalysts, as well as methods for the preparation of both the ligands and corresponding catalysts.
  • the carbene compounds of the present invention are stable, and exhibit excellent electron donating activity. Furthermore, the inventors have elucidated the structure of selected compounds and complexes of the present invention. In preferred embodiments, the increased steric impact and electron donating ability of the carbene compounds of the present invention presents significant advantages.
  • the novel electronic framework of the compounds of the present invention gives rise to a nucleophilic carbene centre capable of acting as a strong ⁇ -donor ligand.
  • the carbene compounds of the present invention are preferably suitable for use in conjunction with many different transition metals to generate complexes that exhibit catalytic activity, including but not limited to olefin metathesis, C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation, and atom transfer radical polymerization (ATRP) catalysis.
  • transition metals including but not limited to olefin metathesis, C-H bond activation, C-C bond formation, C-H bond formation, C-O bond formation, C-N bond formation, and atom transfer radical polymerization (ATRP) catalysis.
  • ATRP atom transfer radical polymerization
  • the transition metals that may be used to generate the catalysts of the present invention include, but are not limited to, Ti, Zr, Al, Rh, Pd, Ni, Ru, Pt, Cr, Fe, Ir and Cu, and other related transition metals.
  • the chemical properties of the carbene compounds of the present invention including steric considerations and a high electron donating activity, are expected to permit successful production of a wide variety of useful catalysts.
  • These catalysts may particularly include transition metals such as Ru, Rh, Pd, and Pt, which are generally known in the art to generate useful catalysts for organic synthesis.
  • the properties of the carbene compounds of the present invention may further permit the successful generation of catalysts comprising Cu or Ni.
  • the present invention provides important opportunities for the development of catalysts comprising far less expensive transition metals, which are nonetheless catalytically active and useful for a range of chemical reactions.
  • the present invention further provides at least two general methods for the synthesis of the carbene compounds of the present invention.
  • the first method involves the production of an N-substituted perimidine, followed by quaternization of the N '-position and deprotonation.
  • the second method involves the reaction of an N,N' disubstituted diamino naphthalene (or other ring structure) to form a corresponding NN'-perimidinium salt, followed by deprotonation.
  • Each method presents advantages.
  • the first method can involve less steps, but includes a quaternization step, which may limit the overall reaction.
  • the second method may involve more steps, but the need for quaternization is avoided.
  • EXAMPLE 1 General experimental Details on Carbene Precursors, Isolated Carbenes, Metal Complexes of Carbenes and Catalysis with these Complexes. All manipulations concerning the preparation of carbenes were carried out in either a nitrogen filled dry box or under nitrogen using standard Schlenk techniques. For these reactions, solvents were sparged with nitrogen then dried by passage through column of activated alumina using an apparatus purchased from Anhydrous Engineering. Deuterated dimethyl sulfoxide, chloroform, and benzene were purchased from Aldrich Chemical Company and in the case of C 6 D 6 was dried by vacuum transfer from potassium.
  • the invention provides for the preparation of novel carbenes of type shown in formula II begins with the reaction of NN -disubstituted diaminonaphthalenes 9 with triethylorthoformate in acidic solution to yield the N.N'- perimidinium salts (2) (Scheme 1).
  • These salts can be prepared in near quantitative yields with a variety of counterions depending on the acid employed in the reaction or by ion exchange.
  • Free, neutral carbene 3 was accessed from the perimidinium cation via clean and rapid deprotonation with Li ⁇ (SiMe 3 ) 2 and was easily crystallized from diethylether. Attempts to deprotonate 2 with NaOtBu led to nucleophilic addition of the alkoxide anion and formation of 4.
  • Compound 4 was also cleanly generated by the addition oftBuOH to 3.
  • ⁇ angle upon moving from the five-membered ring to the six-membered ring geometry.
  • Typical values of ⁇ for structures of type A/B are 122- 123°. 3(a),1 °
  • the observed value in 3 averages 115.5°, which is the smallest of the three angles around the N centres. This results in an increased steric impact of the nitrogen substituents on the C car bene centre and a concomitant effect of the reactivity of this centre and of metal complexes of 3.
  • Rh(I) metal centre Upon coordination to the Rh(I) metal centre, several clear changes are observed in the NMR signatures for 3.
  • Rh-C car bene bond distance of 2.06(1)A is considerably longer than those reported for (COD)RhCl(A)) (2.021(4)A, 2.023(2)A). 11,12 This reflects the steric congestion that was designed into 3.
  • the cis- geometry for 6 is supported by the appearance of two 13 C NMR signals for the CO carbons and by IR spectroscopy, which shows two CO stretching vibrations of similar intensity at 1985 and 2073 cm “1 .
  • N,N'-diisopropyl-l,8-diaminonaphthalene 1.52g, 6 mmol
  • triethyl orthoformate 8.50 g, 54 mmol
  • formic acid 4.08 g, 77 mmol
  • the solution was then degassed (freeze/pump/thaw) and then stirred at 80°C overnight. All volatiles were removed under vacuum and the yellow solid was dissolved in THF and cooled to 4°C.
  • the 1,3-diisopropylperimidinium formate (1.0 g, 2.6 mmol) was added to 10 ml of a NaO ⁇ /NaCl solution (0.51 M and 5.0 M respectively) in a separatory funnel.
  • the aqueous layer was extracted repeatedly with 10 ml aliquots of C ⁇ 2 CI 2 until the organic layer showed very little yellow colour.
  • the crude product obtained by removal of solvent under vacuum was purified by crystallization from a CH 2 C1 2 solution layered with diethyl ether (0.50 g, 65 % yield).
  • Visible signals other than DMSO are at ⁇ l ⁇ .9, 20.2, 30.7, 52.5, 54.5, 108.1, 112.4, 122.8, 123.5, 124.0, 125.4, 128.0, 128.5, 131.7, 137.5, 149.7, 151.9, 162.3.
  • the structure of 1- isopropyl -3-(2- methylpyridyl) perimidinium Tosylate is shown in Figure 6 (anion not shown).
  • the 1-isopropylperimidine (0.6g, 2.9 mmol) and a,a '-dibromo-p-xylene (0.378g, 1.4 mmol) were dissolved in approximately 30 ml of toluene and refluxed for 6 hours.
  • EXAMPLE 23 [a,a '-di(l-p-CH C 6 H CH 3 perimidinium) ort/ ⁇ o-xylene]dibro ⁇ nide
  • l-(p-CH 2 C 6 H 4 CH 3 ) perimidine 0.43 g, 0.00158 moles
  • toluene approximately 25 mL
  • the flask was equipped with a condenser and the solution was heated in an oil bath to 100 °C.
  • a '-dibromo-o-xylene (0.209 g, 0.00079 moles) was added. The reaction proceeded overnight. The precipitate was collected via suction filtration (0.34 g, 53 %).
  • the reaction proceeded for 48 hours.
  • the precipitate was collected via suction filtration (0.67 g, 90 %).
  • LiHMDS lithium bis(trimethylsilyl)amide
  • EXAMPLE 32 Preparation of l-'Pr-3-/>-CH 2 C 6 H 5 -perimidin-2-ylidene l-'Pr-3-Bn perimidinium bromide (l.Og, 2.6 mmol) was added to LiHMDS (0.43g, 2.6 mmol) in a total of about 60 ml of solvent mixture (THF/PhCl). The product, a pale brown viscous liquid, was isolated by extraction with toluene and drying under vacuum (0.76g, 2.5 mmol, 96%).
  • EXAMPLE 34 Preparation of l-cycloheptyl-3-p-CH 2 C 6 H 4 CH 3 perimidin-2-ylidene l- ⁇ ep-3-p-CH 2 C 6 H 4 CH 3 perimidinium bromide (0.535g, 1.2 mmol) was added to LiHMDS (0.20g, 1.2 mmol) in a total of about 25 ml of solvent mixture (THF/PhCl). The product, an off-white solid, was isolated by extraction with hexane and drying under vacuum (0.408g, 92 %).
  • the present invention further encompasses multidentate transition metal ligands, comprising two or more carbene compounds according the invention, and one or more linking moieties comprising alkyl and / or aromatic groups via R and / or R 1 .
  • multidentate transition metal ligands comprising two or more carbene compounds according the invention, and one or more linking moieties comprising alkyl and / or aromatic groups via R and / or R 1 .
  • the structure of one such compound has been determined generally in accordance with the methods previously described.
  • This preferred compound has the following general formula:
  • metal complexes of carbenes - Metal coordination could be done either by in situ deprotonation of the perimidinium cation followed by metallation, or by deprotonation and metallation in one concerted step using a metal complex with ligands capable of deprotonating the perimidinium cation.
  • R aryl, alkyl or a mixture of aryl and alkyl
  • the catalysts for this reaction are one of several different metal complexes with carbene ligand. Both components are necessary for catalytic transformation. More specifically, the catalyst systems consist of one of the metal compounds Pd(OAc) 2 , Ni(COD)2, or Cul in the presence of carbene and a base (NaO l Bu or K 2 CO 3 ). Excellent yields (>90%) and a robust catalyst system were obtained with Cul/carbene in a 1 : 1 ratio used in ether solvents. The following metal complex has been prepared as part of the inventors' investigation of these and related CN bond transformations (the structure of which is shown in Figure 7: Scheme 12
  • Catalysts based on metal complexes of the carbene are effective in the activation of aryl C-F bonds and in the cross- coupling of these aryl halides with nucleophilic reagents such as aryl Grignard reagents (e.g. Kumada coupling).
  • nucleophilic reagents such as aryl Grignard reagents (e.g. Kumada coupling).
  • aryl Grignard reagents e.g. Kumada coupling
  • the cross-coupling of 4-fluorotoluene with phenyl Grignard results in the formation of 4-methylbiphenyl when catalyzed by a mixture of Ni reagents and carbene. These reactions require the presence of a catalyst.
  • Carbene chemistry from fleeting intermediates to powerful reagents G. Bertrand, Ed. Marcel Dekker, New York, 2002. Carbenes M. Jones, R. A. Moss, Eds. Wiley, New York, 1973 and 1975, vols. 1 and 2. 2. Bourissou, D.; Guerret, O.; Gabba ⁇ , F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39.

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Abstract

La présente invention concerne des composés carbène à base de perimidine présentant une activité élevée de don d'électrons. Les composés de l'invention sont particulièrement utiles comme ligands pour former des complexes de métaux de transition. Ces complexes peuvent avoir une action catalytique pour une gamme étendue de réactions chimiques désirables dans le cadre d'une synthèse organique.
PCT/CA2004/001781 2003-10-01 2004-10-01 Ligands carbene et leur utilisation WO2005030782A2 (fr)

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US8492552B2 (en) 2007-06-20 2013-07-23 Agency For Science, Technology And Research N-heterocyclic carbene metallacycle catalysts and methods
CN111393395A (zh) * 2020-04-02 2020-07-10 太原理工大学 一种小球藻转移c=n双键的方法
CN115260252A (zh) * 2022-08-26 2022-11-01 大连理工大学 一种新型呸啶型配合物的合成方法及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119660A1 (en) * 2001-10-02 2003-06-26 Herrmann Wolfgang A. Novel transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030119660A1 (en) * 2001-10-02 2003-06-26 Herrmann Wolfgang A. Novel transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ALDER R.W. ET AL. CHEM. COMMUN. 1999, pages 241 - 242 *
ALDER R.W. ET AL.: 'Perkin trans. 1' J. CHEM. SOC. 2001, pages 1586 - 1593 *

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EP2463266A1 (fr) * 2009-08-07 2012-06-13 Wako Pure Chemical Industries, Ltd. Procédé de production d'un sel d'ammonium bis-quaternaire, et nouvel intermédiaire
JPWO2011016523A1 (ja) * 2009-08-07 2013-01-17 和光純薬工業株式会社 ビス第４級アンモニウム塩の製造法及び新規中間体
EP2463266A4 (fr) * 2009-08-07 2013-03-13 Wako Pure Chem Ind Ltd Procédé de production d'un sel d'ammonium bis-quaternaire, et nouvel intermédiaire
US8716513B2 (en) 2009-08-07 2014-05-06 Wako Pure Chemical Industries, Ltd. Process for production of bis-quaternary ammonium salt, and novel intermediate
EP2821395A3 (fr) * 2009-08-07 2015-01-21 Wako Pure Chemical Industries, Ltd. Nouvel ester d'acide disulfonique en tant qu'additif pour un électrolyte de batterie secondaire au lithium
JP2015071618A (ja) * 2009-08-07 2015-04-16 和光純薬工業株式会社 ジスルホン酸エステル誘導体
CN111393395A (zh) * 2020-04-02 2020-07-10 太原理工大学 一种小球藻转移c=n双键的方法
CN111393395B (zh) * 2020-04-02 2022-12-27 太原理工大学 一种小球藻转移c=n双键的方法
CN115260252A (zh) * 2022-08-26 2022-11-01 大连理工大学 一种新型呸啶型配合物的合成方法及应用
CN115260252B (zh) * 2022-08-26 2024-01-26 大连理工大学 一种新型呸啶型配合物的合成方法及应用

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