GB2537416A - Process - Google Patents

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GB2537416A
GB2537416A GB1506555.0A GB201506555A GB2537416A GB 2537416 A GB2537416 A GB 2537416A GB 201506555 A GB201506555 A GB 201506555A GB 2537416 A GB2537416 A GB 2537416A
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branched
alkyl
aryl
linear
optionally substituted
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Gulyas Henrik
Frater Georg
Ondi Levente
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Ximo AG
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Ximo AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • 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
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

A compound of the formula II: wherein A is either oxygen or substituted nitrogen; B is optionally substituted- pyrrole, pyrazole or indole; or B is OR4, wherein R4 is selected from optionally substituted alkyl, SiAr3 in which Ar is optionally substituted aryl; optionally substituted aryl or heteroaryl; or, in the case in which B is also OR4, the two moieties OR4 may together form a ring; or R4 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded; R1 and R2 are independently selected from H, alkyl and optionally substituted aryl, , with the proviso that only one of R1 and R2 is H; R3 is a substituent, or one or both R3 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded. The compounds are stable and permit the easy in situ generation of metathesis catalysts.

Description

PROCESS
This disclosure relates to metal complexes and to a process of preparing them.
Complexes of molybdenum and tungsten have been used as catalysts for certain chemical reactions, including olefin synthesis. One type is the so-called Schrock catalyst, a typical example of which is shown below: While such catalysts have proved effective, they lack stability in air, which makes them more difficult to handle and restricts their usefulness.
Me2t1( IL. o.-,: Ph Mc
CF EX.
A number of remedies have been suggested, one of which is to dissolve or disperse the catalysts 20 in an inert material such as paraffin wax A typical example of this approach may be found in US patent publication No. 2005/0288257.
In a more recent approach, it has been proposed that such catalysts may be stabilised for use in air by means of complexing them with bidentate N-heterocycles, such as 2,2'-bipyridine and 1,10-phenanthroline. Such an air stable adduct is not active catalytically, but the catalyst may be released by exposure to a Lewis acid, such as zinc chloride, plus heat. This approach is described in Angew. Chem. 'MEd. 2011, 50, 7829-7832. and in PCT published application WO 2012/116695. The resulting metal complex has the Formula (I): in which M is W or Mo and X and Y are the same or different.
It has now been found that a group of these catalysts may be provided by an especially convenient method. There is therefore provided a method of providing in an aprotic solvent a metathesis catalyst, comprising exposing to the solvent a compound of the formula II in which A is selected from 0, N-R, N-O-R and N-N-O-R, in which R is selected from the group consisting of C1-05 alkyl linear or branched; aryl, optionally substituted with one or more substituents selected 5 from C1-05 alkyl linear or branched, halogen and C(Halogen)3; -NR3R6, in which R3,R6 are independently selected from C1-05 alkyl linear and branched; and aryl; B is selected from pyrrole, pyrazole and indole, optionally substituted with one or more C1-05 alkyl linear or branched and C1-05 alkoxy linear or branched; or B is OR4, in which R4 has the significance given below, in which the two moieties -0R4 are the same or different; R1 and R2 are independently selected from H, alkyl and aryl, the aryl being optionally substituted with one or more substituents selected from C1-05 alkoxy, halogen and CF3, with the proviso that only one of Ri and R2 is H; R3 is selected from H, alkyl, aryl, OR, alkoxycarbonyl, perfluorinated alkylaryl NR2 and CN, or one or both R3 may represent a functionalised solid surface to which the compound of Formula II is 15 covalently bonded; R4 is selected from C1-05 linear or branched alkyl, optionally substituted with halogen and phenyl, the phenyl being optionally substituted with C1-05 linear or branched alkyl, C1-05 linear or branched alkoxy, halogen and heteroaryl; SiAr3 in which Ar is aryl, optionally substituted with halogen and CF3; aryl or heteroaryl, optionally substituted with one or more of phenyl and halogen, which phenyl may also be substituted with one or more of Cl-CS alkyl linear or branched; or, in the case in which B is also OR4, the two moieties OR4 may together form a ring; or R4 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded; in a concentration of from 0.00001M to 0.5M, in the absence of Lewis acid.
The provision of a metathesis catalyst by the dissolution of a compound of the type hereinabove described in a solvent without the need for the addition of Lewis acid is a surprising and useful feature that has not previously been demonstrated and that is the property of a relative small selection of such compounds.
By "exposing to the solvent" is meant bringing the compound into contact with the solvent so that the metathesis catalyst is released into the solvent. In one aspect, this means dissolving the compound of Formula II in the solvent. In another aspect, the compound of Formula II is covalently bonded to a functionalised solid surface by means of at least one of the moieties R3 or R4, which surface is then brought into contact with the solvent, under such conditions that the catalyst is released.
Functionalised solid surfaces are well known to and used by the art, typically in sheet or particulate form. Typical examples include silica, alumina and carbon, the last-named particularly in the form of nanotubes.
In particular embodiments, R4 is selected from the moieties SiPh3; -C(CF3)2 R, in which R is selected from C1-C10 linear or branched alkyl, phenyl, and Br Particular examples of compounds include compounds A-I, as shown in the accompanying examples.
Some of the abovementioned compounds are novel. There is therefore also provided a compound of Formula II, in which at least one of the following conditions is fulfilled: A is selected from the group consisting of 0, N-O-R and N-N-O-R, in which R has the significance hereinabove defined; (ii) B is indole or pyrazole; It is a feature of the compounds above-described that the desired catalytic metal complex is 20 produced simply by dissolving the compound of formula (II) in solvent.
GENERAL SYNTHESIS OF THE COMPOUNDS TYPE II
Isolated or in situ-generated catalyst W(A)(B)(0R4)(CR1R2) (0.5 mmol) was dissolved in benzene or toluene (5 mL). The bidentate N-heterocyle (0.5 mmol) was added as a solid. The residues of the protecting agent was washed from its vial into the reaction mixture with benzene or toluene (1 mL). The reaction mixture was stirred at room temperature for 30 min. An aliquote was taken from the reaction mixture, the solvent was removed from it in vacuum, an NMR sample was prepared from the residue in CaDa, and it was analyzed by IN NMR. In the case of fluorine containing molecules 19F NMR analysis was also performed. The NMR spectra showed an equilibrium mixture of the targeted compound II, the 14-electron catalyst W(A)(B)(0R4)(CR1R2) and an equimolar amount of the non-coordinated bidentate N-heterocyle. The reaction mixture was concentrated to 0.2-1 mL, upon which in many cases the targeted product started precipitating. Pentane (3 to 10 mL) was added to the mixture to initiate or complete precipitation of the product. Precipitation of the product further shifted the equilibrium towards the association of W(A)(B)(0R4)(CR1R2) and the bidentate N-heterocyle, usually resulting in excellent yields. The solid II was isolated by filtration, washed with pentane, and dried either in N2 stream or in vacuum. The NMR spectra of the adduct II was concentration and temperature dependent, in accordance with the stability constant of adduct In use, the compounds are exposed to an aprotic solvent in order to release the catalyst. The solvents most appropriate to release the catalyst from the compound of Formula II without the use of Lewis acids are all organic aprotic solvents in which the compound of Formula II is soluble. Typical examples include benzene, toluene, methylene chloride and hexane, and the compound of Formula II is dissolved therein, or, if bonded to a soild substrate, is exposed thereto, in a concentration of from 0.00001M to 0.5M, particularly from 0.0001-0.01M. Upon exposing the compound of Formula II, the bidentate N-heterocycle dissociates, and the catalytically active species is released without the need for addition of Lewis acid, previously required.
Although the process of catalytic species generation can work at room temperature (25"C), it can, in many cases, be enhanced by raising the temperature. Whether elevated temperature will enhance the rate of catalyst release will depend on a number of factors, but the skilled person can, in every case, determine the necessary parameters for optimum catalyst release, with only routine experimentation. In cases in which elevated temperature does enhance catalyst release, greatly elevated temperatures are generally not required, in many cases no higher than 90"C being needed for essentially complete catalyst release. In a particular embodiment, the temperature is between 25°C and 70t. This is true of all the compounds A-I of the worked examples.
The resulting complexes are useful in metathesis reactions, for example, in ring-opening and ring-closing methathesis, cross-metathesis and ring-opening methathesis polymerisation (ROMP) reactions. There is therefore also provided a catalysed methathesis reaction, comprising the provision of a metathesis catalyst by means of the exposure of a compound of Formula II to an aprotic solvent.
The disclosure is further defined with reference to the following non-limiting examples, which 30 describe particular embodiments.
Example 1
Synthesis of the compound A
S i Pr Ar: i Pr
I,...NAr A Ph3SiC,*.w
V Ph3Si
W(CHCMe2Ph)(NANOSiPh3)2(Ar = 2,6-diisopropyl-phenyl) (417 mg, 0.4 mmol) (B. C. Bailey, R. R. Schrock, S. Kundu, A. S. Goldman, Z. Huang, M. Brookhart, Organometallics 2009, 28, 355-360) and 2,2'-bipyridine (62.5 mg, 0.4 mmol) were transfered into a vial. Toluene (3 mL) was added. A deep red homogeneous solution was formed immediately. The solution was stirred at RT overnight. Pentane (2.5 mL) was added, and the vial was transferred into the freezer. No crystallization could be initiated, the compound precipitated as an oil. The vial was removed from the fridge, and left in the box at room temperature. Crystallization of the product started spontaneously in a few hours. Deep orange crystals. Yield: 436 mg (91%).
1H-NMR (CEDE): 6 -0.09 (br, 3H, CH3CHCH3), 0.84 (br, 6H, CH3CHCLIE), 1.21 (s, 3H, CH3 neophylidene), 1.38 (br, 3H, CH3CHCLI3), 2.38 (s, 3H, CI-13 neophylidene), 3.52 (br, 1H, , CH3CHCH3), 4.59 (br, 1H, CH3CHCH3), 6.17 (iii, 2H, H3-,H5-BIF9Y), ), 6.45 (ddd, 3JHH = 8.2, 7.5 Hz, 4JHH = 1.5 Hz, 1H, H4-BIPY), 6.56 (m, 1H, H3'-BIPY), 6.66 (m, 2H, H4',H5'-BIPY), 6.77 (t, 3JHH= 7.5 Hz, 1H, N-Ar Cpara-H), 6.87 (m, 6H, Si(1)Phes Cmerd-H), 6.93 (d, 3JHH= 7.5 Hz,2H, N-Ar Cifieu-H), 7.06 (m, 3H, Si(1)PhE Cpara-H), 7.13 (m, 6H, Si(2)PhE Cm-H), 7.20 (m, 1H, neophylidene Ph Cpara-H), ), 7.22 (m, 3H, Si(2)Ph3Cpara-H), 7.35 (m, 6H, Si(1)Ph3C0H.-H), 7.43 (m, 1H, neophylidene Ph Cnieta-H), 7.83 (m, 2H, neophylidene Ph Corte-H), 8.18 (m, 7H, Si(2)Ph3 C0-H, H6-BIPY), 9.75 (m, 1H, H6'-BIPY), 10.43 ppm (s, 2JwH= 6.5 Hz, 1H, W=CH).
Example 2
Synthesis of the compound B The bispyrrolide precursor W(CHCMe2Ph)(NArtme)(Me2Pyr)2 (Ardime = 2,6-dimethylphenyl, Me2Pyr = 2,5-dimethylpyrrolide) (317 mg, 0.508 mmol) was dissolved in benzene (5 mL). Ph(CF3)2COH (86 microL, 0.508 mmol) was added, and the reaction mixture was stirred for an hour at room temperature. An aliquot of the reaction mixture was analyzed by 1H and 19F NMR. Complete conversion was observed into the desired intermediate. 2,2'-Bipyridine (79 mg, 0.508 mmol) was added. The reaction mixture turned deep red. It was stirred for on hour at room temperature. An aliquot was analyzed by 1H and 19F NMR. An equilibrium mixture could be observed between the bipyridine adduct and the MAP complex The solvent evaporated in vacuum, almost to dryness. . Pentane was added, and the precipitated solid was triturated, resulting in a brick colored powder.
The product was isolated by filtration, washed with pentane, and dried in N2 flow. Light brick colored solid. Yield: 429 mg (91%).
1H-NMR (C61:16): 1.25 (s, 3H, CH3), 1.73(s, 3H, CH3), 1.90 (s, 3H, CH3), 2.34 (s, 3H, CH3), 2.46 (s, 3H, CH3), 2.63 (s, 3H, CH3), 6.28 (m, 1H, BIPY), 6.32 (m, 1H, BIP'Y), 6.59-7.35 (neophylidene Ph, arylimido aromatic, Me2Pyr aromatic), 7.63 (broad d, Jryry = 7.4 Hz, 2H BIPY), 7.73 (broad d, Jryry = 7.8 Hz, 2H, BIP'Y), 8.49 (broad d, JHH = 5.7 Hz, 1H BIP'Y), 9.27 (broad d, JHH = 5.1 Hz, 1H, BIP'Y), 11.98 ppm (s, 1H, VV=CH,2JwH=10.2 Hz).
19F-NMR (C3D8): -75.7 (q, 3F, CF3,4JFF = 10 Hz), -68.7 ppm (q, 3F, CF3, 4JFF = 10 Hz).
Example 3
Synthesis of the compound C The bispyrrolide precursor W(CHCMe2Ph)(NArdllP)(Me2Pyr)2 (Ardil9, = 2,6-diisopropylphenyl, Me2Pyr = 2,5-dimethylpyrrolide) (340 mg, 0.5 mmol) (T. Kreickmann, S. Arndt, R. R. Schrock, P. Mueller, Organometallics 2007, 26, 5702) was dissolved in benzene (5 mL). Ph(CF3)2COH (84 microL, 0.5 mmol) was added, and the reaction mixture was stirred for an hour at room temperature An aliquot of the reaction mixture was analyzed by 1H and "F NMR, and the MAP intermediate was found to be of >98% purity. 2,2-bipyridyine (78 mg, 0.5 mmol) was added. The reaction mixture was stirred for 20 min at room temperature. An aliquot was analyzed by 1H and 19F NMR. Both methods confirmed a ca. 50% conversion of the intermediate into the desired 18-electron complex. After stirring the reaction mixture for 16 hours more, another sample was taken, and analyzed by NMR. The analysis showed no further progress of the reaction. The majority of the solvent was removed in vacuum to shift the equilibrium towards the formation the desired product. Pentane was added, and the precipitated solids were isolated by filtration. Ocher solid. Yield: 388 mg (79%).
1H-NMR (C6D3): 0.43 (d, 34H = 6.9Hz, 3H, CH3CHCH3), 0.51 (d, 3JHH = 6.9 Hz, 3H, CH3CHCH3), 1.18 (d, 3JHH = 6.4 Hz, 3H, CH3CHCH3), 1.39 (d, 3JHH = 6.7 Hz, 3H, CH3CHCH3), 1.84 (s, 3H, CH3), 2.16 (s, 3H, CH3), 2.25 (s, 3H, CH3), 2.56 (pseudo sept, 3JHH = ca. 6.9 Hz, 1H, CH3CHCH3), 2.71 (s, 3H, CH3), 4.15 (sept, 34-H = ca. 6.6 Hz, 1H, CH3CHCH3), 6.25 (ddd, 1H, BIPY), 6.31 (ddd, 1H, BIPY), 6.56-7.40 (neophylidene Ph, arylimido aromatic! Me2Pyr aromatic), 7.63 (broad d, Jryry = 7.8 Hz, 2H BIPY), 7.75 (broad d, JHH = 7.6 Hz, 2H, BIPY), 8.70 (broad d, JHH = 5.6 Hz, 1H BIPY), 9.36 (broad d, JHH = 5.4 Hz, 1H, BIPY), 12.04 ppm (s, 1H, W=CH,2JwH=10 Hz).
19F-NMR (C6D6): -75.3 (broad q, 3F, CF3, 4,4 = 11 Hz), -69.0 ppm (q, 3F, CF3, 4JFF= 11 Hz).
Example 4
Synthesis of the compound D The compound was synthesised via the general synthetic route we described for the synthesis of Examples 2 and 3 as described above. Orange solid. Yield: 82%.
1H-NMR (C6D6): 10.20 ppm (s, 1H, W=C.
1.27 (s, 3H, CH3 neophylidene, 2.05 (s, 3H, CH3 neophylidene, 2.58 (s, 3H, CH3 2,5-dimethylpyrrole), 3.18 (s, 3H, CH3 2,5-dimethylpyrrole), 7.79 (d, 1H, H2 BIPY), 8.90 (d, 1H, H2' BIPY), 10.21 ppm (s, 1H, 2JwH= 7 Hz, W=CH).
Example 5
Synthesis of the compound E The compound was synthesised via the general synthetic route we described for the synthesis of 20 Examples 2 and 3 as described above. Light orange solid. Yield: 96%.
1H-NMR (C6D6): 1.39 (s, 3H, CH3), 1.59 (s, 3H, CH3), 1.72 (s, 3H, CH3), 1.74 (s, 3H, CH3), 1.94 (s, 3H, CH3), 2.35 (s, 3H, CH3), 2.50 (s, 3H, CH3), 2.69 (s, 3H, CH3), 6.58-7.31 (neophylidene Ph, arylimido aromatic, 2,5-dimethylpyrrole aromatic, DMBIPY aromatic), 7.66-7.77 (m, 4H), 8.54 (broad s, 1H, H2 DMBIPY), 9.22 (broad s, 1H, H2 DMBIPY), 11.99 ppm (s, 1H, W=CH,2JwH=10.1 Hz).
Example 6
Synthesis of the compound F The compound was synthesised via the general synthetic route we described for the synthesis of Examples 2 and 3 as described above. Orange solid. Yield: 92%.
1H-NMR (C6D3): 0.49 (d, 3JHH = 6.9Hz, 3H, CH3CHCH3), 0.61 (d, 3JHH = 6.9 Hz, 3H, CH3CHCH3), 5 1.20 (d, 3JHH = 6.3 Hz, 3H, CH3CHCH3), 1.41 (d, 3JHH = 6.8 Hz, 3H, CH3CHCF12), 1.84 (s, 3H, CH3), 2.19 (s, 3H, CH3neophylidene), 2.25 (s, 3H, CH3), 2.64 (pseudo sept, = ca. 6.9 Hz, 1H, CH3CHCH3), 2.77 (s, 3H, CH3), 4.17 (pseudo sept, 3JHH = ca. 6.6 Hz, 1H, CH3CHCH3), 6.59 (m, 2H), 6.72-7.35 (neophylidene Ph, arylimido aromatic, Me2Pyr aromatic, DMBIPY aromatic), 7.60 (broad m, 2H), 7.79 (broad m, 2H), 8.63 (broad s, 1H, H2' DMBIPY), 9.28 (broad s, 1H,H2 DMBIPY), 12.21 ppm (s, 1H, W=CH,2../wH=10.0 Hz).
Example 7
Synthesis of the compound G Br W(CHCMe2Ph)(NArme)(Me2Pyr)2 (Me2Pyr = 2,5-Me2C4H2N, Arm° = dimethylphenyl) (312 mg, 0.5 mmol) was dissolved in benzene (5 mL). Ph(CF3)2COH (84 microL, 0.5 mmol) was added, and the reaction mixture was stirred for an hour at room temperature. An aliquot of the reaction mixture was analyzed by 1H NMR and found to be of a purity of >98%. 2,2'-Dibromo-2,2'bipyridine (DBBIPY, 157 mg, 0.5 mmol) dissolved in benzene (3 mL) was added. The reaction mixture turned red immediately. The vial of the DBBIPY was rinsed into the reaction mixture with benzene (2 x 1 mL). The reaction mixture was stirred for 1 hour at room temperature. An aliquot was analyzed by 1H NMR. An equilibrium mixture of the product, free MAP complex, and free DBBIPY could be observed. The solvent was evaporated. Pentane (3-4 mL) was added. The product was not soluble, but it did not solidified either. Upon the addition of small amount of toluene (ca. 2 mL) the product turned into an orange powder. The mixture was moved into the freezer. Next morning the product was isolated by filtration, carried out in the freezer. Yield: 473 mg (87%). According to 1H NMR it contains small amount of dimethylpyrrolide. It was mounted on a fritt, moved to the freezer, and having cooled for an hour, it was washed with precooled pentane (in the freezer). It was dried in vacuum. Brick red solid. Yield: 433 mg (80%).
1H-NMR (C6D6): 1.22 (s, 3H, CH3), 1.68 (s, 3H, CH3), 1.83 (s, 3H, CH3), 2.21 (s, 3H, CH3), 2.41 (s, 3H, CH3), 2.58 (s, 3H, CH3), 6.22 (dd, J=5.9, 1.7 Hz, 1H, H3 DiBrBIPY)-6.3-8.0 (aromatic), 8.18 (d, J=6.1 Hz, 1H, H2' DiBrBIPY), 8.91 (d, J=5.9Hz, 1H, H2 DiBrBIPY), 11.78 ppm (s, 1H, W=CH, 2JwH=10.5 Hz).
Example 8
Synthesis of the compound H Br Br W(CHCMe2Ph)(NArPr)(Me2Pyr)(0C(CF3)2Ph) (Me2Pyr = 2,5-Me2C4H2N, ArPr = diisopropylphenyl) (83 mg, 0.1 mmol) was dissolved in benzene (1 mL). 4,4'-Dibromo2,2'-bipyridine (31 mg, 0.1 mmol) dissolved in benzene (1 mL) was added. The reaction mixture turned red immediately. The rest of the dibromobipyridyl was rinsed into the reaction mixture with benzene (1 mL), and it was stirred for an hour at RT. An aliquot of the reaction mixture was analyzed by 1H NMR.
The solution was concentrated in vacuum, upon which the product started to crystallize yielding 20 nice needle-like crystalls. The reaction mixture was cooled to room temperature, and cold pentane was added, which yielded a brick red precipitate. It was isolated by filtration, and washed with cold pentane. Brick red solid. Yield: 93 mg (81%).
1H-NMR (C6D6): 1.78 (s, 3H, CH3 neophylidene), 2.05 (s, 3H, CH3 neophylidene), 2.15 (s, 3H, CH3 2,5-dimethylpyrrole), 2.66 (s, 3H, CH3 2,5-dimethylpyrrole), 4.06 (pseudo sept, 1H, CH3CHCH3), 6.23 (dd, 1H, H3 DiBrBIPY), 6.51 (s, 2H, CH 2,5-dimethylpyrrole), 6.65 (dd, 1H, H3' DiBrBIPY), 8.44 (dd, 1H, H2' DiBrBIPY), 9.02 (dd, 1H, H2 DiBrBIPY), 12.00 ppm (s, 1H, W=CH). 12F-NMR (C6D6): -69.0 (q, 3F, CF3, 4JFF=11 Hz), -75.1 ppm (q, 3F, CF3, 4JFF=11 Hz).
Example 9
Synthesis of the compound I To the yellow W(CHCMe2Ph)(NArP1)(2-0Et-Ind)(0-2,3,5,6-Ph4C8Br) (2-0Et-Ind = 2-Ethoxyindolide, ACP1 = diisopropylphenyl) (30 mg, 0.0266 mmol) dissolved in benzene (3 mL), 2,2'-bipyridine (4.2 mg, 0.0266 mmol) was added. The rest of 2,21-bipyridine, from the walls of the vial, was rinsed into the reaction mixture with benzene (1 mL). The yellow solution turned light orange. The solution was stirred for 30 min at room temperature, and then it was concentrated in vacuum till dryness. Orange solid. Yield: quantitative.
1H-NMR (C8D8): 6 0.13 (d br, 3H, CH3CHCH3), 0.28 (d br, 3H, CH3CHCLI3), 0.72 (d br, 3H, 10 CH3CHCH3), 1.75 (s, 3H, CH3 neophylidenel, 1.82 (s, 3H, CH3 neophylidene), 3.30 (br, 1H, CH3CHCH3), 4.17 (br, 1H, CH3CHCH3), 5.87 (s, 3H, H3 2-etcodindole), 7.75 (d, 1H, H2 BIP'Y), 8.05 (d, 1H, H2' BIPY), 11.64 ppm (s br, 1H, W=CH).
Example 10
Demonstration of the effect of dilution on catalyst generation Compound C as prepared in Example 3 was dissolved in deuterobenzene at different dilutions and catalyst release measured at room temperature. The catalyst release is expressed as percentage by mole of the mole of the original compound C. The results for C6D6 solution of C at 25 °C are 20 shown in the following table Dilution catalyst release 0.05M 23 0.01M 47 0.001M 83 The release increases with dilution.
Example 11
Demonstration of the effect of temperature on catalyst generation. Ii
Compounds C and F as prepared in Example 3 and 6 respectively were dissolved in deuterobenzene at 0.01M concentration and the generation of the catalytic species was monitored by NMR at a range of temperatures. The catalyst release is expressed as mole percentage of the original compound C. The results are shown in the following table Temperature (C) catalyst release (C) catalyst release (F) 47 21 76 44 89 62 60 95 77 >99 89 As can be seen, the proportion of liberated catalyst rises substantially with temperature, with essentially complete release at 70'C
Example 12
Comparison of the catalytic performance of an autoactivating catalyst and the corresponding catalyst species in the homometathesis of allylbenzene.
The dissolution-activated species was D, prepared in Example 4 above. The catalytic species released, D', was prepared separately Ph Ph I Br Ph In the homometathesis of allylbenzene the catalytic activities (expressed in catalytic turnovers) of D and D-proved identical at substrate:catalyst ratios 100 and 1000. At a substrate:catalyst ratio 5000, D provided slightly less turnover than did D". The stereoselectivites (E/Z ratios) were identical practically in all cases.
catalyst glove box. RT, 16h General procedure: catalyst 0.01mmol, substrate 1-50mmol, 16 hours at room temperature, solvent toluene (except*, where no solvent was present).
Catalyst Substrate/catalyst ratio (wt) Conversion (%) E/Z TON D 100 92.6 86/14 93 D 100 92.5 86/14 93 D' 1000 54.9 86/14 549 D 1000 56.3 07/13 563 D!* 5000 69.9 86/14 3495 D" 5000 54.2 87/13 2710

Claims (5)

  1. Claims: I. A method providing in an aprotic solvent a metathesis catalyst, comprising exposing to the solvent of a compound of the formula IIS IIin which A is selected from 0, N-R, N-O-R and N-N-O-R, in which R is selected from the group consisting of C1-05 alkyl linear or branched; aryl, optionally substituted with one or more substituents selected from C1-05 alkyl linear or branched, halogen and C(Halogen)3; -NR3Re, in which R3,R8 are independently selected from C1-05 alkyl linear and branched; and aryl; B is selected from pyrrole, pyrazole and indole, optionally substituted with one or more C1-05 alkyl linear or branched and C1-05 alkoxy linear or branched; or B is OR4, in which R4 has the significance given below, in which the two moieties -OR, are the same or different; R1 and R2 are independently selected from H, alkyl and aryl, the aryl being optionally substituted with one or more substituents selected from C1-05 alkoxy, halogen and CF3, with the proviso that only one of R1 and R2 is H; R3 is selected from H, alkyl, aryl, OR, alkoxycarbonyl, perFluorinated alkylaryl NR2 and CN, or one or both R3 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded; R4 is selected from C1-05 linear or branched alkyl, optionally substituted with halogen and phenyl, the phenyl being optionally substituted with C1-05 linear or branched alkyl, C1-05 linear or branched alkoxy, halogen and heteroaryl; SiAr3 in which Ar is aryl, optionally substituted with halogen and CF3; aryl or heteroaryl, optionally substituted with one or more of phenyl and halogen, which phenyl may also be substituted with one or more of C1-05 alkyl linear or branched; or, in the case in which B is also OR4, the two moieties OR4 may together form a ring; or R4 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded;in a concentration of from 0.00001M to 0.5M, in the absence of Lewis acid.
  2. 2 Method according to daim 1, in which R4 is selected from the moieties: -SiPh3; -C(CF3)2R, in which R is selected from C1-C10 alkyl, linear or branched and phenyl, optionally substituted; and
  3. 3. Method according to claim 1, in which the compound of formula II is exposed to the solvent in a concentration of from 0.0001-0.01M.
  4. 4. Method according to claim 1, in which the compound of Formula II is exposed to the solvent at a temperature of from 25"C-90"C, particularly from 25C-70°C.A catalysed methathesis reaction, comprising the provision of a metathesis catalyst by means of the exposure of a compound of Formula II to an aprotic solvent in a concentration of from 0.00001M to 0.5M in the absence of Lewis acid: R4 in which A is selected from 0, N-R, N-O-R and N-N-O-R, in which R is selected from the group consisting of Cl-05 alkyl linear or branched; aryl, optionally substituted with one or more substituents selected from C1-05 alkyl linear or branched, halogen and C(Halogen)3; -NR5R6, in which R5,R6 are independently selected from C1-05 alkyl linear and branched; and aryl; B is selected from pyrrole, pyrazole and indole, optionally substituted with one or more C1-05 alkyl linear or branched and C1-05 alkoxy linear or branched; or B is OR4, in which R4 has the significance given below, in which the two moieties -ORL are the same or different; R1 and R2 are independently selected from H, alkyl and aryl, the aryl being optionally substituted with one or more substituents selected from C1-05 alkoxy, halogen and CF3, with the proviso that only one of R, and R2 is H; R3 is selected from H, alkyl, aryl, OR, alkoxycarbonyl, perFluorinated alkylaryl NR2 and CN, or one or both R3 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded;IIR4 is selected from C1-05 linear or branched alkyl, optionally substituted with halogen and phenyl, the phenyl being optionally substituted with C1-05 linear or branched alkyl, C1-05 linear or branched alkoxy, halogen and heteroaryl; SiAr3 in which Ar is aryl, optionally substituted with halogen and CF3; aryl or heteroaryl, optionally substituted with S one or more of phenyl and halogen, which phenyl may also be substituted with one or more of C1-05 alkyl linear or branched; or, in the case in which B is also OR4, the two moieties OR4 may together form a ring; or R4 may represent a functionalised solid surface to which the compound of Formula II is covalently bonded;
  5. 5. A compound according to Formula II in which at least one of the conditions (i) and 00 is fulfilled: (i) A is selected from the group consisting of 0, N-O-R and N-N-O-R, in which R is selected from the group consisting of C1-05 alkyl linear or branched; aryl, optionally substituted with one or more substituents selected from C1-05 alkyl linear or branched and C(Halogen)3; -NR3R6, in which R3,R3 are independently selected from C1-05 alkyl linear and branched; and aryl; (H) B is indole or pyrazole; the remaining moieties being selected as follows: R1 and R2 are independently selected from H, alkyl and aryl, the aryl being optionally substituted with one or more substituents selected from C1-05 alkoxy, halogen and CF3, with the proviso that only one of R1 and R2 is H; R3 is selected from H, alkyl, aryl, OR, alkoxycarbonyl, perfluorinated alkylaryl NR2 and CN; R4 is selected from C1-05 alkyl linear or branched; halogen (F, Cl, Br); SiPh3; aryl, optionally substituted with one or more of phenyl and halogen, which phenyl may also be substituted with one or more of C1-05 alkyl linear or branched.
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