WO2002044188A1 - Palladacyclic compounds containing phosphorus donor ligands, the ligands and the use of the compounds in c-c coupling reactions - Google Patents

Palladacyclic compounds containing phosphorus donor ligands, the ligands and the use of the compounds in c-c coupling reactions Download PDF

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WO2002044188A1
WO2002044188A1 PCT/GB2001/005198 GB0105198W WO0244188A1 WO 2002044188 A1 WO2002044188 A1 WO 2002044188A1 GB 0105198 W GB0105198 W GB 0105198W WO 0244188 A1 WO0244188 A1 WO 0244188A1
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formula
aryl
cycloalkyl
alkyl
independently selected
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Samantha Louise Hazelwood
Robin Bruce Bedford
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Johnson Matthey Public Limited Company
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    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • 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
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage

Definitions

  • the present invention relates to novel palladacyclic complexes of phosphorus- donor ligands, and novel phosphorus-donor ligands used in the preparation of said complexes. Furthermore the invention relates to the use of said palladacyclic complexes and phosphorus-donor ligands in coupling reactions, for example Suzuki (Scheme 1),
  • This high activity is not limited to metallated phosphorus donor systems - Milstein and co-worker have shown that the metallated imine complex (4) shows excellent activity (H. Weissman and D. Milstein, Chem. Commun., 1999, 1901), whilst Zim et al have shown that the metallated thioether complexes (5) can also be used (D. Zim, A. S. Gruber, G. Ebeling, J. Dupont and A. L. Monteiro, Org. Letts. 2000, 2, 2881).
  • the present invention provides a novel palladacyclic complex of formula (I)
  • R and R may be the same or different and each is independently selected from Ci-6 alkyl, C 3 . 6 cycloalkyl or aryl;
  • (R) n indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from C ⁇ alkyl, C 3 . 6 cycloalkyl, aryl or any heteroatomic function;
  • X is halo, acetate or trifluoroacetate;
  • Y is O, S, NR or CR R wherein R and R 4 are each independently selected from hydrogen, . 6 alkyl, C 3 .
  • heteroatomic function we mean any substituent wherein the atom attached to the benzene ring is a heteroatom, for example Cl, F, NO 2 , NH 2 , a substituted amino group, OH or ether group.
  • complexes of formula (I) include complexes of formula (IA), (IB) and (IC):
  • R , R , (R) n and Y are as hereinbefore defined, with a palladium salt.
  • suitable palladium salts include PdCl 2 , [PdCl 2 (NCPh) 2 ] and [ ⁇ Pd(OAc) 2 ⁇ 3 ] and [Pd(TFA) 2 ] (TFA is trifluoroacetate).
  • the reaction is carried out in a suitable solvent, for example toluene or THF, at elevated temperature, for example at the reflux temperature of the solvent.
  • R 1 , R 2 , (R) n , Y and X are as hereinbefore defined, and which is in itself an active catalytic species.
  • Compounds of formula (IN) are also novel and accordingly a further aspect of the invention provides a compound of formula (IV) and its use in C-C coupling reactions.
  • Ligands of formula (V) are novel and accordingly provide a further aspect of the invention.
  • Ligands of formula (V) may be prepared by methods that are similar to the known procedures for preparation of compounds of formula (II). Due to the identification of ligands of formula (V), it is postulated that during the process of a Suzuki coupling reaction, compounds of formula (I) react with a boronic acid substrate to form a new species of formula (VI),
  • R 1 , R 2 , (R) n and Y are as hereinbefore defined. This complex is only formed in situ and it is not possible to isolate it.
  • the application of ligands of formula (N) to C-C coupling reactions is a further aspect of the invention.
  • the reaction may be carried out by mixing the coupling reaction reactants together with a ligand of formula (V) and a suitable palladium salt, for example PdCl 2 , [ ⁇ Pd(OAc) 2 ⁇ 3 ], [Pd 2 (dba) 3 ], [PdCl 2 (PhC ⁇ ) 2 ] or [Pd(TFA) 2 ], such that the catalyst species is prepared in situ.
  • a suitable palladium salt for example PdCl 2 , [ ⁇ Pd(OAc) 2 ⁇ 3 ], [Pd 2 (dba) 3 ], [PdCl 2 (PhC ⁇ ) 2 ] or [Pd(TFA) 2 ], such that the catalyst species is prepared in situ.
  • the ligand of formula (V) may be separately reacted with a suitable palladium compound to form a complex of formula (III), which depending on the reaction conditions may further react to give a complex of formula (I) or formula (IV).
  • the C-C coupling reaction may be carried out by mixing the reactants together with the complex of formula (I), (III) or (IV) in a suitable solvent and heating for an appropriate period, as described below.
  • complexes of formula (I), (III) or (IV) and ligands of formula (II) or (V) are attached to solid supports.
  • the solid support is preferably a hydrocarbon resin in the form of beads or fibres.
  • the R 1 , R 2 , R 3 , R 4 , (R) n or (R)' n substituents may contain groups that are suitable for ion exchange, eg a SO 3 H group could be ion exchanged onto a cationic support.
  • the R 1 , R 2 , R 3 , R 4 , (R) n or (R)' n substituents may contain groups that are suitable for covalent coupling to a support, eg a NH 2 group could form an amide or imine linkage.
  • the R 1 , R 2 , R 3 , R 4 , (R) n or (R)'êt substituents may contain a polymerisable group such as a vinyl group allowing the complex or ligand to be incorporated directly into a polymer support during a polymerisation process.
  • a complex of formula (I), (II) or (IN) is charged, then the complex may be ion exchanged onto a suitable support.
  • 2,4-di-tert-butylphenol (4.7g, 22.8mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm 3 ). The phenol was then stirred in dry degassed toluene (80cm 3 ), chlorodiphenylphosphine (4.0cm 3 , 22.3mmol) and dry degassed triethylamine (3.5cm 3 , 25.1mmol) were added. A white precipitate of Et 3 N + HCr was immediately evolved. The mixture was heated at reflux temperature overnight.
  • 2,4-di-tert-butylphenol (6.6257g, 32.1mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm 3 ). The phenol was then stirred in dry degassed toluene (80cm 3 ), chlorodiisopropylphosphine (5.5cm 3 , 34.5mmol) and dry degassed triethylamine (5.0cm 3 , 35.8mmol) were added. A white precipitate of Et 3 N HCl " was immediately evolved. The mixture was heated at reflux temperature overnight.
  • Phenol (5.33g, 32.1mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm 3 ). The phenol was then stirred in dry degassed toluene (80cm 3 ), chlorodiphenylphosphine (6.0cm 3 , 33.4mmol) and dry degassed triethylamine (5.0cm 3 , 35.8mmol) were added. A white precipitate of Et 3 N + HCl " was immediately evolved. The mixture was heated at reflux temperature overnight.
  • 2-phenylphenol (4.75 lg, 0.0279mol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm 3 ). The phenol was then stirred in dry degassed toluene (100cm 3 ), chlorodiphenylphosphine (5.0cm 3 , 0.0279mol) and dry degassed triethylamine (4.5cm 3 ) were added. A white precipitate of EtsN ⁇ HCl " was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm 3 ) was added to facilitate precipitation of the Et3N + HCl " , which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed petrol and then the solvent was removed in vacuo yielding a yellow oil (9.48g, 0.0268mol, 95.9% yield).
  • 2-phenylphenol (5.345g, 0.0314mol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm 3 ). The phenol was then stirred in dry degassed toluene (100cm 3 ), chlorodiisopropylphosphine (5.0cm 3 , 4.795g, 0.0314mol) and dry degassed triethylamine (5.0cm 3 ) were added. A white precipitate of Et 3 N + HC ⁇ " was immediately evolved. The mixture was heated at reflux temperature overnight.
  • Activated magnesium (0.487g, 0.020mol) was stirred in dry degassed ether (40cm 3 ). The mixture was cooled in an ice bath (2-3°C) and 2-phenylbenzylbromide (5g, 0.0202mol) was added dropwise. The mixture was then allowed to warm to room temperature where it was stirred for an hour. The green-grey solution was filtered through a cannula to remove any unreacted magnesium and then the solution was cooled in an ice bath and chlorodiphenylphosphine (4.42g, 0.020mol) was added dropwise. A precipitate was evident but the mixture was stirred at room temperature overnight. The precipitate was removed by filtration through Celite under nitrogen and the filtrate was concentrated in vacuo to yield a white solid (4.868g, 0.0138mol, 69% yield).
  • reaction was stirred in an argon atmosphere at 100°C for 24 hours, with an intermediate sample taken after 5 hours.
  • Samples of reaction liquor were centrifiiged before an aliquot of 0.5ml was taken, diluted with N,N-dimethylacetamide (0.25ml) and analysed by GC (GC column CP-SIL 5, 10m x 0.53mm capillary, temperature programmed 130 - 300°C).
  • Table 2 Heck coupling of 4-bromoacetophenone with n-butyl acrylate catalysed by palladium phosphinite complexes.

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  • Organic Chemistry (AREA)
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Abstract

Novel palladacyclic complexes and novel phosphorus-donor ligands are disclosed. The invention further relates to the use of said complexes and ligands in coupling reactions, for example Suzuki and Heck coupling reactions.

Description

PALLADACYCLIC COMPOUNDS CONTAINING PHOSPHORUS DONOR LIGANDS, THE LIGANDS AND THE USE OF THE COMPOUNDS IN C-C COUPLING REACTIONS
The present invention relates to novel palladacyclic complexes of phosphorus- donor ligands, and novel phosphorus-donor ligands used in the preparation of said complexes. Furthermore the invention relates to the use of said palladacyclic complexes and phosphorus-donor ligands in coupling reactions, for example Suzuki (Scheme 1),
Heck (Scheme 2) and Stille (Scheme 3) coupling reactions.
Figure imgf000002_0001
Scheme 1. The Suzuki biaryl coupling reaction.
[cat]
Rl— X + ^^ R2 base
Scheme 2: The Heck reaction
[cat] Rl— X + R2Sn(R3)3 *■ Rl— R2
Scheme 3: The Stille reaction
There has recently been considerable interest in the synthesis of new, high activity palladium-based catalysts that can be used in low concentration in the Suzuki reaction since such catalysts have the potential to be used in industrial systems. In particular, palladacyclic catalysts in which a ligand coordinates to the metal centre through both a donor atom and metallated carbon have shown considerable promise. Beller et al (M. Beller, H. Fischer, W. A. Herrmann, K. Ofele and C. Brossmer, Angew. Chem. Int. Ed. Engl., 1995, 34, 1848) demonstrated that the dimeric complex (1)
Figure imgf000002_0002
shows good activity, whilst Bedford et al have shown that the palladated triarylphosphite complex (2) and the bis(phosphinite)PCP-pincer complexes (3) show excellent activity (D. A. Albisson, R. B. Bedford, S. E. Lawrence and P. N. Scully, Chem. Commun., 1998, 2095 and R. B. Bedford, S. M. Draper, P. N. Scully and S. L. Welch, New J. Chem., 2000, 745).
Figure imgf000003_0001
Figure imgf000003_0002
acetate
This high activity is not limited to metallated phosphorus donor systems - Milstein and co-worker have shown that the metallated imine complex (4) shows excellent activity (H. Weissman and D. Milstein, Chem. Commun., 1999, 1901), whilst Zim et al have shown that the metallated thioether complexes (5) can also be used (D. Zim, A. S. Gruber, G. Ebeling, J. Dupont and A. L. Monteiro, Org. Letts. 2000, 2, 2881).
Figure imgf000003_0003
X = trifluoroacetate The present inventors have now discovered a new class of palladacyclic compounds which show excellent activity as coupling catalysts, for example in Suzuki, Heck and Stille reactions.
Accordingly, the present invention provides a novel palladacyclic complex of formula (I)
Figure imgf000004_0001
wherein R and R may be the same or different and each is independently selected from Ci-6 alkyl, C3.6 cycloalkyl or aryl; (R)n indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from C^ alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function; X is halo, acetate or trifluoroacetate; and Y is O, S, NR or CR R wherein R and R4 are each independently selected from hydrogen, .6 alkyl, C3.6 cycloalkyl or aryl, with the proviso that (i) when R1 and R2 are both phenyl, X is Cl, Br or acetate and the benzene ring is unsubstituted, then Y is not CH2, and (ii) when R1 and R2 are both 'butyl, X is Br and the benzene ring is unsubstituted, then Y is not CH2.
By the term "heteroatomic function" we mean any substituent wherein the atom attached to the benzene ring is a heteroatom, for example Cl, F, NO2, NH2, a substituted amino group, OH or ether group.
Preferably, Y is O. Specific complexes of formula (I) include complexes of formula (IA), (IB) and (IC):
Figure imgf000004_0002
Figure imgf000005_0001
Complexes of formula (I) may be prepared by the reaction of a compound of formula (II)
Figure imgf000005_0002
1 wherein R , R , (R)n and Y are as hereinbefore defined, with a palladium salt. Examples of suitable palladium salts include PdCl2, [PdCl2(NCPh)2] and [{Pd(OAc)2}3] and [Pd(TFA)2] (TFA is trifluoroacetate). The reaction is carried out in a suitable solvent, for example toluene or THF, at elevated temperature, for example at the reflux temperature of the solvent.
Compounds of formula (II) may be prepared by analogous methods to those in the literature for compounds of formula (II) wherein the benzene ring is unsubstituted.
Compounds of formula (II) can also be reacted with palladium salts under milder conditions than those described above, for example at room temperature, to form the novel complexes of formula (III)
Figure imgf000005_0003
wherein R1, R2, (R)n and Y are as hereinbefore defined, and X' is halo, for example chloro. Complexes of formula (III) are novel and accordingly provide a further aspect of the invention. Although the cis form of complex (III) is illustrated, the complex may exist as a mixture of cis and trans forms.
Compounds of formula (III) may be converted to compounds of formula (I) under suitable conditions described below.
Compounds of formula (I) and formula (III) show good activity in C-C coupling reactions, for example Suzuki, Heck and Stille coupling reactions and accordingly a further aspect of the invention provides the use of compounds of formula (I) or formula (III) in C-C coupling reactions, more particularly in Suzuki, Heck and Stille coupling reactions.
Furthermore, there is evidence that using a combination of a palladium complex of formula (I) and the corresponding ligand of formula (II) may have a beneficial effect and lead to even better TON values (TON = Turnover Number (the number of reactions cycles performed by the catalyst)), than when using a compound of formula (I) alone. When a compound of formula (I) and the corresponding ligand of formula (II) are used together, they react to form a compound of formula (IV)
Figure imgf000006_0001
wherein R1, R2, (R)n, Y and X are as hereinbefore defined, and which is in itself an active catalytic species. Compounds of formula (IN) are also novel and accordingly a further aspect of the invention provides a compound of formula (IV) and its use in C-C coupling reactions.
During a coupling reaction, a ligand of formula (V)
Figure imgf000007_0001
wherein R1, R2, (R)n and Y are as hereinbefore defined and (R')n indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from C^ alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function, has been identified. Ligands of formula (V) are novel and accordingly provide a further aspect of the invention. Ligands of formula (V) may be prepared by methods that are similar to the known procedures for preparation of compounds of formula (II). Due to the identification of ligands of formula (V), it is postulated that during the process of a Suzuki coupling reaction, compounds of formula (I) react with a boronic acid substrate to form a new species of formula (VI),
Figure imgf000007_0002
wherein R1, R2, (R)n and Y are as hereinbefore defined. This complex is only formed in situ and it is not possible to isolate it.
The application of ligands of formula (N) to C-C coupling reactions is a further aspect of the invention. The reaction may be carried out by mixing the coupling reaction reactants together with a ligand of formula (V) and a suitable palladium salt, for example PdCl2, [{Pd(OAc)2}3], [Pd2(dba)3], [PdCl2(PhCΝ)2] or [Pd(TFA)2], such that the catalyst species is prepared in situ. In an alternate aspect of the invention, the ligand of formula (V) may be separately reacted with a suitable palladium compound to form a complex of formula (III), which depending on the reaction conditions may further react to give a complex of formula (I) or formula (IV). The C-C coupling reaction may be carried out by mixing the reactants together with the complex of formula (I), (III) or (IV) in a suitable solvent and heating for an appropriate period, as described below.
In a particular embodiment of the invention, complexes of formula (I), (III) or (IV) and ligands of formula (II) or (V) are attached to solid supports. The solid support is preferably a hydrocarbon resin in the form of beads or fibres. There are a number of ways the compound may be attached to the support. The R1, R2, R3, R4, (R)n or (R)'n substituents may contain groups that are suitable for ion exchange, eg a SO3H group could be ion exchanged onto a cationic support. The R1, R2, R3, R4, (R)n or (R)'n substituents may contain groups that are suitable for covalent coupling to a support, eg a NH2 group could form an amide or imine linkage. Alternatively the R1, R2, R3, R4, (R)n or (R)'„ substituents may contain a polymerisable group such as a vinyl group allowing the complex or ligand to be incorporated directly into a polymer support during a polymerisation process. Finally, if a complex of formula (I), (II) or (IN) is charged, then the complex may be ion exchanged onto a suitable support.
Complexes of formula (I), (III) or (IN) and ligands of formula (II) or (V) that are attached to solid supports show particular advantages in coupling reactions. A major advantage is the ease of recovery of the catalyst and the possibility that the catalyst may be reused. Additionally, the risk of contamination of the product by either Pd or ligand is reduced and this is particularly useful in the synthesis of pharmaceutical products.
The invention will now be described by way of examples only, which are intended to illustrate and not to limit the invention. Synthesis of the ligands of formula (II).
Ligand 1 - 2,4-di-tert-butylphenyl diphenylphosphinite C^H^OP
Figure imgf000009_0001
2,4-di-tert-butylphenol (4.7g, 22.8mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm3). The phenol was then stirred in dry degassed toluene (80cm3), chlorodiphenylphosphine (4.0cm3, 22.3mmol) and dry degassed triethylamine (3.5cm3, 25.1mmol) were added. A white precipitate of Et3N+HCr was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm3) was added to facilitate precipitation of the Et3N+HCl", which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed petrol and then the solvent was removed in vacuo yielding a white solid (7.809g, 20mmol, 90% yield).
31P NMR spectrum: δ (CDC13): 108.51 (s) ppm.
1H NMR spectrum: δ (CDC13): 7.63 (m, 4H), 7.40 (m, 6H), 7.36 ( d, 1H, 5JHH = 1.92Hz), 7.12 (dd, 1H, 5JHH = 1.92 Hz, 3JHH = 5.77Hz), 7.05 (dd, 1H, 3JHH = 5.77Hz, 4JPH = 2.75Hz), 1.39 (s, 9H), 1.32 ( s, 9H) ppm.
Ligand 2 - 2,4-di-tert-butylphenyl diisopropylphosphinite C?oH3 OP
Figure imgf000009_0002
2,4-di-tert-butylphenol (6.6257g, 32.1mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm3). The phenol was then stirred in dry degassed toluene (80cm3), chlorodiisopropylphosphine (5.5cm3, 34.5mmol) and dry degassed triethylamine (5.0cm3, 35.8mmol) were added. A white precipitate of Et3N HCl" was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm3) was added to facilitate precipitation of the Et3N+HCr, which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed petrol and then the solvent was removed in vacuo yielding a white oil (8.495g, 26.3mmol, 82% yield).
31P NMR spectrum: δ (CDC13): 138.4 (s) ppm.
1H NMR spectrum: δ (CDCI3): 7.62 (dd, 1H, 3JHH = 14.26Hz, JPH = 6.6Hz), 7.40 (d 1H, JPH = 2.47Hz), 7.21 (dd, 1H, 3JHH = 14.26Hz, JPH = 2.75Hz), 2.22 (m, 2H), 1.52 (s, 9H), 1.40 (s, 9H), 1.25 (m, 12H) ppm.
Ligand 3 - Phenyl diphenylphosphinite CπHisOP
Figure imgf000010_0001
Phenol (5.33g, 32.1mmol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm3). The phenol was then stirred in dry degassed toluene (80cm3), chlorodiphenylphosphine (6.0cm3, 33.4mmol) and dry degassed triethylamine (5.0cm3, 35.8mmol) were added. A white precipitate of Et3N+HCl" was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm3) was added to facilitate precipitation of the EtsNΗcr, which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed petrol and then the solvent was removed in vacuo yielding a yellow oil (8.128g, 29.21mmol ,91% yield).
3 J11P NMR spectrum: δ (CDCI3): 111.2 (s) ppm. 1H NMR spectrum: δ (CDC13): 7.09 (m, 1H), 7.21 (m, 2H), 7.34 (m, 2H) 7.46 (m, 6H), 7.68 (m, 4H) ppm.
Synthesis of the ligands of formula (V).
Figure imgf000011_0001
Figure imgf000011_0002
2-phenylphenol (4.75 lg, 0.0279mol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm3). The phenol was then stirred in dry degassed toluene (100cm3), chlorodiphenylphosphine (5.0cm3, 0.0279mol) and dry degassed triethylamine (4.5cm3) were added. A white precipitate of EtsN^HCl" was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm3) was added to facilitate precipitation of the Et3N+HCl", which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed petrol and then the solvent was removed in vacuo yielding a yellow oil (9.48g, 0.0268mol, 95.9% yield).
31P NMR spectrum: δ (CDCI3): 113.36 (s) ppm. 1H NMR spectrum: δ (CDCI3): 7.55 (m, 6H), 7.35 (m, 8H), 7.18 (m, 5H) ppm.
Ligand 5 - 2-phenylphenyl diisopropylphosphinite QιsH23OP
Figure imgf000011_0003
2-phenylphenol (5.345g, 0.0314mol) was azeotropically dried with portions of dry degassed toluene (3 x 10cm3). The phenol was then stirred in dry degassed toluene (100cm3), chlorodiisopropylphosphine (5.0cm3, 4.795g, 0.0314mol) and dry degassed triethylamine (5.0cm3) were added. A white precipitate of Et3N+HCι" was immediately evolved. The mixture was heated at reflux temperature overnight. The reaction was cooled, dry degassed petrol (30cm3) was added to facilitate precipitation of the EtsN^HCl", which was removed by filtration through a pad of Celite under an atmosphere of nitrogen. The precipitate was washed with portions of dry degassed ether and then the solvent was removed in vacuo yielding a yellow oil (7.40g, 0.0258mol, 82.3% yield).
31P NMR spectrum δ (CDC13): 151.46 ppm.
1H NMR spectrum: δ (CDCI3): 7.68 (m, 2H), 7.48 (m, 6H), 7.17 (t, 1H), 1.95 (m, 2H), 1.15 (m, 12H) ppm.
Figure imgf000012_0001
Activated magnesium (0.487g, 0.020mol) was stirred in dry degassed ether (40cm3). The mixture was cooled in an ice bath (2-3°C) and 2-phenylbenzylbromide (5g, 0.0202mol) was added dropwise. The mixture was then allowed to warm to room temperature where it was stirred for an hour. The green-grey solution was filtered through a cannula to remove any unreacted magnesium and then the solution was cooled in an ice bath and chlorodiphenylphosphine (4.42g, 0.020mol) was added dropwise. A precipitate was evident but the mixture was stirred at room temperature overnight. The precipitate was removed by filtration through Celite under nitrogen and the filtrate was concentrated in vacuo to yield a white solid (4.868g, 0.0138mol, 69% yield).
31P NMR spectrum: δ (CDCI3): -8.11 ppm.
1H NMR spectrum: δ (CDCI3): 7.36 (m, 4H), 7.26 (m, 15H), 3.45 (s, 2H) ppm. Synthesis of the complexes of formula (I).
Complex 1 - cis and trans 2,4-di-tert-butylphenyldiphenylphosphinite palladium complex riPd^niPrOCfiH^ -Bu^CCgH^ }?!.
Palladium chloride (0.25g, 1.4mmol) and 2,4-di-tert-butylphenyl diphenylphosphinite (0.55 lg, 1.41mmol) in dry degassed toluene (40cm3) were heated at reflux temperature for 4 hours. After which time the solvent was removed in vacuo, yielding an orange solid, which was dissolved in dichloromethane and filtered through Celite. Then ethanol was added and the product crystallised. The product was recrystallised from dichloromethane/ethanol yielding an orange-yellow solid (0.389g, 0.366mmol, 52% yield).
31P NMR spectrum: δ (CDC13): 155.24 (s); 154.76 (s) ppm. 1H NMR spectrum: δ (CDCI3) at -50°C: 7.90 (m, 8H); 7.46 (m, 12H); 7.37 (s, 2H); 7.06 (s, 2H); 1.31 (s, 24H); 1.30 (s, 12H) ppm.
IR spectrum: (KBr disc): μc-H 3067 (aryl), μC-H 2865 (methyl group), μc=c 1600 (aromatic), μc-H 1399 (But), μpd-ci 507.5 cm"1.
Complex 2 - cis and trans 2,4-di-tert-butylphenyldiisopropylphosphinite palladium
Figure imgf000013_0001
Palladium chloride (1.50g, 8.68mmol) and 2,4-di-tert-butylphenyl diisopropylphosphinite (2.80g, 8.68mmol) in dry degassed dioxane (40cm3) were heated at reflux temperature for 18 hours. The mixture was filtered through Celite and the solvent was removed leaving a red orange solid. The solid was dissolved in dichloromethane and crystallised with methanol. The orange solid was recrystallised from dichloromethane and methanol (2.01g, 2.169mmol, 50% yield).
31P NMR spectrum: δ (CDCI3): 203.4 (s), 202.7 (s) ppm.
1H NMR spectrum: δ (CDCI3): 7.06 (dd, 1H), 6.98 (s, 1H), 2.37 (m, 2H), 1.40 (m, 12H), 1.32 (s, 9H), 1.26 (s, 9H) ppm. Complex 3 - cis and trans phenyl diphenylphosphinite palladium complex r{Pd(cmpfoc6H4γc.H 2n2ι.
Bis(benzonitrile)dichloropalladium (0.50g, 1.304mmol) and phenyl diphenylphosphinite (0.390g, 1.4mmol) were heated at reflux temperature for 18 hours in dry degassed tetrahydrofuran. After which time, the solvent was removed in vacuo, yielding an orange solid. The solid was dissolved in dichloromethane and filtered through Celite. The filtrate was concentrated on a rotary evaporator, ethanol added and the product crystallised. The yellow product was recrystallised from dichloromethane and ethanol (0.352g, 0.42mmol, 64.4% yield).
31P NMR spectrum: δ (CDC13): 154.79 (s); 154.20 (s) ppm.
1H NMR spectrum: δ (CDCI3): 7.55 (m, 8H); 7.47 (m, 12H); 7.05 (m, 2H); 6.90 (m, 6H) ppm.
Synthesis of complexes of formula (IN)
Complex 4 - cis and trans r(PdrCniPrOC6H2-2,4-But2)(C6H5 P(OC6H 2,4- BuVlz(CήH )z}1.
In a 50cm3 round bottomed flask were placed [{Pd(Cl){P(OC6H2-2,4-
Bu2)(C6H5)2}}2] (O.lg, 0.094mmol), 2,4-di-tert-butylphenyl diphenylphosphinite
(0.071g, 0.182mmol) in dichloromethane (6cm3). The mixture was stirred for 30 minutes. Ethanol (10cm3) was added and then the solvents were concentrated yielding a grey solid (0.056g, 0.060mmol, 66% yield).
31P ΝMR spectrum: δ (CDC13): 155.3 (d, 2JPP = 42.39Hz), 151.3 (d, 2JPP = 475Hz), 113.0 (d, 2JpP = 475Hz), 110.0 (d, 2JPP = 42.39Hz) ppm. 1H ΝMR spectrum: δ (CDCI3): 7.92 (m, 12H), 7.41 (m, 12H), 7.05(m, 2H), 6.70 (m, 2H),1.48 (s, 9H), 1.42 (s, 9H), 1.40 (s, 9H), 1.30 (s, 9H) ppm. Complex 5 - cis and trans r{Pd(CmP(OCgHr2,4-BuV, (CH(CH 3)7HP(OCfiHr2,4-
Figure imgf000015_0001
In a 50cm3 round bottomed flask were placed [{Pd(Cl){P(OC6H2-2,4- But2(CH(CH3)2)2}2] (O.lg, 0.108mmol), 2,4-di-tert-butylphenyl diisopropylphosphinite
(0.070g, 0.216mmol) in dichloromethane (6cm3). The mixture was stirred for
30 minutes. Ethanol (10cm3) was added and then the solvents were concentrated yielding a grey solid (0.057g, 0.0725mmol, 46% yield).
3IP NMR spectrum: δ (CDC13): 200.39 (d, 2JPP = 198.36Hz), 132.25 (s), 128.03 (d, 2JPP = 652Hz), 60.76 (d, 2JPP = 996Hz) ppm.
1H NMR spectrum: δ (CDCI3): 7.75 (dd, 1H), 7.30 (m, 1H), 7.18(dd, 1H), 6.60 (d, 1H), 3.05 (m 2H), 2.45 (m, 2H), 1.40 (m, 30H), 1.30 (m, 30H), ppm.
Synthesis of complexes of formula (III)
Figure imgf000015_0002
In a schlenk tube under an atmosphere of nitrogen were placed PdCl2(NCPh)2 (0.2g, 0.5214mmol) and 2,4-di-tert-butylphenyl diphenylphosphinite (0.455g,
1.165mmol). Dried degassed dichloromethane (30cm3) was added and the yellow solution was stirred at room temperature for 4 hours, after which time degassed hexane
(20cm3) was added and the solution was concentrated in vacuo to yield a yellow solid
(0.439g, 0.458mmol, 87.9% yield).
31P NMR spectrum: δ (CDCI3): 102.85 ppm
1H NMR spectrum: δ (CDCI3): 7.783 (m, 10H), 7.692 (m, 2H), 7.385 (m, 14H) 1.397(s,
9H), 1.368 (s, 9H) ppm.
Catalysis
Suzuki Catalysis
In a three-necked round bottomed flask under an atmosphere of nitrogen were placed K2CO3 (2.764g, 20mmol), the aryl halide (lOmmol) and phenylboronic acid (1.829g, 15mmol). In a second three-necked round bottomed flask under an atmosphere of nitrogen were placed hexadecane solution (3cm3, 0.068M, 0.204mmol), catalyst and ligand solutions (1cm3), these combined solutions were frozen and degassed three times. Then they were transferred by cannula into the first three-necked flask, dry degassed toluene (27cm3) was then passed through the cannula to rinse all the catalyst through into the reaction flask. The reaction mixture was then heated at 130°C for 18 hours under an atmosphere of nitrogen. After which time the reaction was cooled in an ice bath and quenched with aqueous hydrochloric acid and extracted with dichloromethane. The combined organic extracts were concentrated to dryness. A solution in dichloromethane was made up and a sample was analysed by GC (Narian GC 3800, Chrompack Capillary Column (WCOT fused silica 25m x 0.25mmID, coating CP-SIL 5CB)).
(Catalyst and ligand solutions made up in dry degassed dichloromethane and tetrahydrofuran respectively.)
Table 1. Suzuki coupling of aryl halides with phenylboronic acid catalysed by palladium phosphinite complexes.
Figure imgf000016_0001
Figure imgf000017_0001
"Determined by GC, based on aryl halide. 24 h reaction time. Alkylboronic Acid Coupling
In a Radleys carousel reactor tube under an atmosphere of nitrogen were placed K3PO (2mmol), 4-bromoanisole (lmmol) and butylboronic acid (1.5mmol). In a schlenk tube under an atmosphere of nitrogen were placed dioxane solution (10ml) and a solution of complex 2 (0.023 lg, 0.5mmol). These solutions were made up in a Glovebox. Then they were transferred into the Radleys reaction tube. Dry degassed dioxane (5cm ) was then added to the reaction tube. The reaction mixture was then heated at 100°C for 18 hours under an atmosphere of nitrogen. After which time the reaction was cooled in an ice bath and quenched with aqueous hydrochloric acid and extracted with dichloromethane. The combined organic extracts were concentrated to dryness. A solution in dichloromethane was made up and a sample was analysed by GC. (Catalyst and ligand solutions made up in dry degassed dioxane respectively.)
75% conversion was achieved at 0.5mol% Pd, which corresponds to a TON of
150. Unlike prior art alkylboronic acid couplings, a stoichiometric amount of either Ag+ or Tl+ was not required.
Heck Catalysis
To reaction vials containing a magnetic follower was added; sodium acetate (0.09g, 1. lmmol), 4-bromoacetophenone solution in N,N-dimethylacetamide (1M, 1ml) and n-butyl acrylate solution in N,N-dimethylacetamide (1.4M,lml). The complexes (O.Olmmol, substrate/catalyst ratio 100:1) were added as a suspension/solution in N,N-dimethylacetamide (1ml). The reaction volume was finally brought up to 4ml with the addition of further N,N-dimethylacetamide. This was to allow for intermediate sampling of the reaction.
The reaction was stirred in an argon atmosphere at 100°C for 24 hours, with an intermediate sample taken after 5 hours. Samples of reaction liquor were centrifiiged before an aliquot of 0.5ml was taken, diluted with N,N-dimethylacetamide (0.25ml) and analysed by GC (GC column CP-SIL 5, 10m x 0.53mm capillary, temperature programmed 130 - 300°C). Table 2. Heck coupling of 4-bromoacetophenone with n-butyl acrylate catalysed by palladium phosphinite complexes.
Figure imgf000019_0001
cResults are reported as percentage of the desired compound formed.

Claims

A compound of formula (I)
Figure imgf000020_0001
wherein R and R may be the same or different and each is independently selected from Cι. alkyl, C3.6 cycloalkyl or aryl; (R)n indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from d-β alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function; X is halo, acetate or trifluoroacetate; and Y is O, S, NR3 or CR3R4 wherein R3 and R4 are each independently selected from hydrogen, C\.(, alkyl, C3.6 cycloalkyl or aryl, with the proviso that (i) when R1 and R2 are both phenyl, X is Cl, Br or acetate and the benzene ring is unsubstituted, then Y is not CH2, and (ii) when R and R are both butyl, X is Br and the benzene ring is unsubstituted, then Y is not CH2.
2. A process for the preparation of a compound according to claim 1, said process comprising the reaction of a compound of formula (II)
Figure imgf000020_0002
wherein R , R , (R)n and Y are as hereinbefore defined, with a palladium salt.
3. The use of a compound according to claim 1 in C-C coupling reactions.
4. A compound of formula (III)
Figure imgf000021_0001
wherein R1 and R2 may be the same or different and each is independently selected from Cj-6 alkyl, C3.6 cycloalkyl or aryl; (R)n indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from C e alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function; X' is halo; and Y is O, S, NR3 or CR3R4 wherein R3 and R4 are each independently selected from hydrogen, CL6 alkyl, C3.6 cycloalkyl or aryl.
5. A process for the preparation of a compound according to claim 4, said process comprising the reaction of a compound of formula (II)
Figure imgf000021_0002
wherein R1, R2, (R)n and Y are as hereinbefore defined, with a palladium salt under mild conditions.
6. The use of a compound according to claim 4 in C-C coupling reactions.
7. A compound of formula (IN)
Figure imgf000021_0003
1 wherein R and R may be the same or different and each is independently selected from -6 alkyl, C3.6 cycloalkyl or aryl; (R)„ indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from hydrogen, Ci-β alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function; X is halo, acetate or trifluoroacetate; and Y is O, S, NR3 or CR3R4 wherein R and R4 are each independently selected from hydrogen, Cι.6 alkyl, C3. cycloalkyl or aryl.
8. A process for the preparation of a compound according to claim 7, said process comprising the reaction of a compound of formula (I) as hereinbefore defined with a compound of formula (II) as hereinbefore defined.
9. The use of a compound according to claim 7 in C-C coupling reactions.
10. A compound of formula (V)
Figure imgf000022_0001
wherein R1 and R2 may be the same or different and each is independently selected from Ci-6 alkyl, C3.6 cycloalkyl or aryl; (R)n and (R')n may be the same or different and each independently indicates from 0 to 4 substituents on the benzene ring wherein each substituent may be the same or different from the others and is independently selected from hydrogen, d-6 alkyl, C3.6 cycloalkyl, aryl or any heteroatomic function; and Y is O, S, NR3 or CR3R4 wherein R3 and R4 are each independently selected from hydrogen, C^ alkyl, C3.6 cycloalkyl or aryl.
11. The use of a compound according to claim 10, in combination with a palladium salt, in C-C coupling reactions.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO2004016710A1 (en) * 2002-08-15 2004-02-26 E.I. Du Pont De Nemours And Company Compounds comprising phosphorus-containing metal complexes
US6963005B2 (en) 2002-08-15 2005-11-08 E. I. Du Pont De Nemours And Company Compounds comprising phosphorus-containing metal complexes
WO2006056608A2 (en) * 2004-11-26 2006-06-01 Phoenix Chemicals Limited Carbonylation process and catalyst therefor
WO2006056608A3 (en) * 2004-11-26 2006-08-03 Stylacats Ltd Carbonylation process and catalyst therefor
CN108368142A (en) * 2015-12-02 2018-08-03 住友化学株式会社 The manufacturing method and palladium complex of aromatic compound
CN108368142B (en) * 2015-12-02 2021-02-19 住友化学株式会社 Method for producing aromatic compound and palladium complex

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