# US 2017/0282170 A9 · Phosphorus-containing catalysts

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- Number: US 2017/0282170 A9
- Document ID: US20170282170A9
- Status: Published application
- Kind: A9
- Application number: 14/913,479
- Filed: 2014-08-29
- Published: 2017-10-05
- Earliest claimed: 2013-08-29
- Assignees: Agency for Science, Technology and Research
- Applicants: Agency for Science, Technology and Research
- Inventors: Charles W. Johannes; Edward G. Robins; Howard Jong; Yee Hwee Lim; Saei Weng Chia; Yong Yang; Anil Podichetty
- Web page: https://patentgrep.com/patent/US20170282170A9

## CPC

- B01J 31/2409: {with more than one complexing phosphine-P atom}
- B01J 31/1875: {Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/2404: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring}
- B01J 31/2414: {comprising aliphatic or saturated rings}
- B01J 31/2495: {Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands}
- C07C 2/861: {the non-hydrocarbon contains only halogen as hetero-atoms}
- C07C 17/361: by reactions involving a decrease in the number of carbon atoms
- C07C 37/18: by condensation involving halogen atoms of halogenated compounds
- C07D 209/10: with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D 295/033: with the ring nitrogen atoms directly attached to carbocyclic rings
- C07D 409/04: directly linked by a ring-member-to-ring-member bond
- C07F 9/5063: {from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds (C07F9/5059 takes precedence)}
- C07F 15/006: {Palladium compounds}
- C07F 15/0066: {without a metal-carbon linkage}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2231/40: Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J 2231/4205: C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J 2231/4211: Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J 2231/4227: with Y= Cl
- B01J 2231/4233: Kumada-type, i.e. RY + R'MgZ, in which Ris optionally substituted alkyl, alkenyl, aryl, Y is the leaving group and Z is halide
- B01J 2231/4261: Heck-type, i.e. RY + C=C, in which R is aryl
- B01J 2231/4266: Sonogashira-type, i.e. RY + HC-CR' triple bonds, in which R=aryl, alkenyl, alkyl and R'=H, alkyl or aryl
- B01J 2231/4277: C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J 2231/4283: using N nucleophiles, e.g. Buchwald-Hartwig amination
- B01J 2531/824: Palladium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The invention provides compounds of general structure I: (Ar1—Ar2—Ar3-E-P(=D)R2-)nMmXnLn″. In this structure: •Ar1, Ar2 and Ar3 are aromatic groups wherein: —Ar1 and Ar3 are in a 1,3 relationship on Ar2, —each of Ar1, Ar2 and Ar3 optionally comprises one or more ring substituents of formula YR′r wherein each Y independently is absent or is O, S, B, N or Si and each R′ is independently H, halogen, alkyl, cycloalkyl, aryl or heteroaryl and r is 1, 2 or 3, where r is 1 if Y is absent or is O or S, 2 if Y is B or N and 3 if Y is Si, —Ar1, Ar2 and Ar3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar1, Ar2 and Ar3 independently has 5, 6 or 7 ring atoms; •E is absent or is selected from the group consisting of O, S, NR″, SiR″2, AsR″2 and CR″2; •M is a complexing metal; •X is selected from the group consisting of H, F, Br, CI, I, OTf, dba (dibenzylidene acetone), OC(═O)CF3 and OAc; •L is selected from the group consisting of PR″2, NR″2, OR″, SR″, SiR″3, AsR″3, alkene, alkyne, aryl and heteroaryl, each of said alkene, alkyne, aryl and heteroaryl being optionally substituted, for example with one or more halogens and/or with one or more R groups as defined herein; •each R is independently alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl or -, heteroaryl; •D is absent or is ═S or —O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length; •each R″ is independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each other than H being optionally substituted, or R″2 is —Z-linker-Z— as defined above; and •m is 0 or 1 or 2; wherein if m is 0, n is 1, n′ and n″ are 0 and -- is absent; and if m is 1 or 2, n is 1 or 2 and n′ and n″ are integers such that the coordination sphere of M is filled, and D is absent.

## Claims

### Claim 1

A compound of structure I:
(Ar1—Ar2—Ar3-E-P(=D)R2—-)nMmXn′Ln″
wherein:
Ar1, Ar2 and Ar3 are aromatic groups wherein:
Ar1 and Ar3 are in a 1,3 relationship on Ar2,
each of Ar1, Ar2 and Ar3 optionally comprises one or more ring substituents of formula YR′r wherein each Y independently is absent or is O, S, B, N or Si and each R′ is independently H, halogen, alkyl, cycloalkyl, aryl or heteroaryl and r is 1, 2 or 3, where r is 1 if Y is absent or is O or S, 2 if Y is B or N and 3 if Y is Si,
Ar1, Ar2 and Ar3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar1, Ar2 and Ar3 independently has 5, 6 or 7 ring atoms;
E is absent or is selected from the group consisting of O, S, NR″, SiR″2, AsR″2 and CR″2;
M is a complexing metal;
X is selected from the group consisting of H, F, Br, Cl, I, OTf, dba (dibenzylidene acetone), OC(═O)CF3 and OAc;
L is absent or is selected from the group consisting of PR″2, NR″2, OR″, SR″, SiR″3, AsR″3, alkene, alkyne, aryl and heteroaryl, each of said alkene, alkyne, aryl and heteroaryl being optionally substituted, for example with one or more halogens and/or with one or more R groups as defined herein, wherein if L is absent, n is not 1;
each R is independently alkyl, cycloalkyl, heterocyclyl, heterocycloalkyl, aryl, heteroaryl, alkyloxy, cycloalkyloxy, heterocyclyloxy, heterocycloalkyloxy, aryloxy or heteroaryloxy;
D is absent or is ═S or ═O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length;
each R″ is independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl, each other than H being optionally substituted, or R″2 is —Z-linker-Z— as defined above; and
m is 0 or 1 or 2; wherein:
if m is 0, n is 1, n′ and n″ are 0 and -- is absent; and
if m is 1 or 2, n is 1 or 2 and n′ and n″ are integers such that the coordination sphere of M is filled, and D is absent.

### Claim 2 (depends on 1)

The compound of claim 1 wherein m is 1 or 2 and M is bonded to a ring atom of Ar3 ortho to E.

### Claim 3 (depends on 1, 2)

The compound of claim 1 or claim 2 wherein E is O or S or NR″.

### Claim 4 (depends on 1, 2, 3)

The compound of any one of claims 1 to 3 wherein n is 1 or 2 and M is selected from the group consisting of Pd, Ni, Pt, Cu, Fe, Co, Au, Ag, Rh, Ir, Ru, Os or Mn.

### Claim 5 (depends on 4)

The compound of claim 4 wherein M is Pd, Ni or Cu.

### Claim 6 (depends on 5)

The compound of claim 5 wherein M is Pd.

### Claim 7 (depends on 1, 2, 3, 4, 5, 6)

The compound of any one of claims 1 to 6 wherein m is 1 or 2 and X is Cl or OAc.

### Claim 8 (depends on 1)

The compound of claim 1 wherein m=0.

### Claim 9 (depends on 1)

The compound of claim 1 wherein m=1.

### Claim 10 (depends on 1)

The compound of claim 1 wherein m=2 and n″ is 0.

### Claim 11 (depends on 1, 2, 3, 4, 5, 6, 7, 9, 10)

The compound of any one of claims 1 to 7, 9 or 10 wherein n=m.

### Claim 12 (depends on 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11)

The compound of any one of claims 1 to 11 wherein each R is independently selected from the group consisting of alkyl, cycloalkyl, aryl and heteroaryl.

### Claim 13 (depends on 12)

The compound of claim 12 wherein each R is alkyl or each is aryl, or one is alkyl and the other is aryl.

### Claim 14 (depends on 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 12)

The compound of any one of claims 1 to 7 or 9 to 12 wherein n″ is 0, M is Pd and n is 2.

### Claim 15 (depends on 1)

The compound of claim 1 wherein Ar1 is phenyl, Ar2 is 2,4,6-trimethylphenyl or 2,4,6-triisopropylphenyl, Ar3 is phenyl, E is O, R attached to P is each alkyl or each is aryl, or one is alkyl and the other is aryl, and n is 1 and either m, n′ and n″ are all 0 or m is 1, n′ is 1 and n″ is 0 and M is Pd.

### Claim 16 (depends on 1)

The compound of claim 1 wherein if E is absent, n is 1 and m, n′ and n″ are all 0.

### Claim 17 (depends on 1)

A process for making a compound of structure I as defined in claim 1, said process comprising reacting a compound of structure II:
Ar1—Ar2—Ar3-E-PR2
wherein Ar1, Ar2 and Ar3, E and R are as defined in claim 1 and Ar1 and Ar3 are in a 1,3 relationship on Ar2,
with a salt or complex of M, optionally in the presence of a liganding species.

### Claim 18 (depends on 17)

The process of claim 17 wherein no liganding species is present, whereby m=2, said process comprising the subsequent step of exposing the compound of structure I in which m=2 to a liganding species so as to produce a compound of structure I in which m=1 and L is said liganding species or is derived therefrom.

### Claim 19 (depends on 17, 18)

The process of claim 17 or claim 18 wherein the liganding species is a phosphine, an amine, an alcohol, a thiol, a silane, an arsine, an olefin, an aromatic compound or a heteroaromatic compound.

### Claim 20 (depends on 17, 18, 19)

The process of any one of claims 17 to 19 wherein M is selected from the group consisting of Pd, Ni, Pt, Cu, Fe, Co, Au, Ag, Rh, Ir, Ru, Os and Mn.

### Claim 21 (depends on 17, 18, 19, 20)

The process of any one of claims 17 to 20 wherein the salt or complex of M is a dba, diene, olefin, allyl, silane, nitrile or organonitrile complex (such as Pd(PhCN)2Cl2, Pd(CN)2 or Pd(MeCN)4(BF4)2 or Pd(COD)(CH2TMS)2 or Pd(NBD)(CH2TMS)2), or a halide or acetate or cyanide salt or a salt of a pseudohalide, e.g. triflate, of M.

### Claim 22 (depends on 20)

The process of claim 20 wherein M is Pd, Ni or Cu.

### Claim 23 (depends on 22)

The process of claim 22 wherein M is Pd.

### Claim 24 (depends on 1, 17, 18, 19, 20, 21, 22, 23)

The process of any one of claims 17 to 23 comprising reacting a compound of structure III:
Ar1—Ar2—Ar3-E-X
wherein Ar1, Ar2 and Ar3 and E are as defined in claim 1 and Ar1 and Ar3 are in a 1,3 relationship on Ar2,
with either:
a compound of structure X—PR2, wherein R is as defined in claim 1 or
a compound of structure X—P(D)R2 wherein R is as defined in claim 1, and subsequently removing the group D, wherein D is ═S or ═O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length
wherein each X is independently selected from the group consisting of H, F, Br, Cl, I, OTf, dba, OC(═O)CF3 and OAc
so as to produce the compound of structure II.

### Claim 25 (depends on 1, 17)

A process for making a compound of structure II as defined in claim 17 comprising reacting a compound of structure III:
Ar1—Ar2—Ar3-E-X
wherein Ar1, Ar2 and Ar3 and E are as defined above and Ar1 and Ar3 are in a 1,3 relationship on Ar2,
with either:
a compound of structure X—PR2, wherein R is as defined in claim 1 or
a compound of structure X—P(D)R2 wherein R is as defined in claim 1, and subsequently removing the group D, wherein D is ═S or ═O or —Z-linker-Z—, where each Z independently is O or NH or N-alkyl and linker is an alkyl chain of 2-5 carbon atoms in length
wherein each X is independently selected from the group consisting of H, F, Br, Cl, I, OTf, dba, OC(═O)CF3 and OAc.

### Claim 26 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25)

The process of any one of claims 17 to 25 wherein each ring in Ar1, Ar2 and Ar3 has independently, 5 or 6 ring carbon atoms.

### Claim 27 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26)

The process of any one of claims 17 to 26 wherein at least one of Ar1, Ar2 and Ar3 is a fused aromatic ring or a fused heteroaryl ring.

### Claim 28 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26)

The process of any one of claims 17 to 26 wherein each of Ar1, Ar2 and Ar3 is monocyclic, e.g. is a phenyl ring.

### Claim 29 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28)

The process of any one of claims 17 to 28 wherein E is O, S, NR″2 or absent.

### Claim 30 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29)

The process of any one of claims 17 to 29 wherein the R groups on P are both alkyl or both are aryl or one R is alkyl and one is aryl.

### Claim 31 (depends on 24, 25)

The process of claim 24 or 25 comprising the step of conducting a metal mediated cross-coupling reaction of a biaryl compound with an aryl compound so as to produce the compound of structure III.

### Claim 32 (depends on 31)

The process of claim 31 comprising reacting a compound of structure IV: Ar1—Ar2A in which A is a leaving group or activating group, e.g. a halogen or a triflate group or a boronic acid or boronic ester, and in which A is meta to Ar1 on Ar2, with a compound of structure XEAr3A or Ar3A in the presence of an electrophile, so as to produce the compound of structure III.

### Claim 33 (depends on 32)

The process of claim 32 wherein A is either an electron donating group or an electron withdrawing group.

### Claim 34 (depends on 17)

The process claim 17 comprising:
providing a 2,4,6-trialkylbiphenyl
halogenating said 2,4,6-trialkylbiphenyl in the 3 position
metallating the resulting halogenated biphenyl and reacting the resulting intermediate with an o-halophenol to form a 2-hydroxy-2′,4′,6′-trialkyl-m-terphenyl, or with an o-dihalobenzene to form a 2-halo-2′,4′,6′-trialkyl-m-terphenyl, and
reacting the m-terphenyl with a base and a halodialkylphosphine or halodiarylphosphine or haloalkylarylphosphine to produce a dialkylphosphinite or diarylphosphinite or alkylarylphosphinite of 2-hydroxy-2′,4′,6′-trialkyl-m-terphenyl respectively or else metallating the m-terphenyl and reacting the resulting intermediate, optionally in the presence of a copper salt and/or lithium salt, and a halodialkylphosphine or halodiarylphosphine or haloalkylarylphosphine to produce a dialkylphosphine or diarylphosphine or alkylarylphosphine respectively, each of said dialkylphosphinite or diarylphosphinite or alkylarylphosphinite or dialkylphosphine or diarylphosphine or alkylarylphosphine being a compound of structure II.

### Claim 35 (depends on 34)

The process of claim 34 wherein, in the step of metallating, the intermediate is reacted with an o-halophenol and the subsequent step comprises reacting the resulting m-terphenyl with a base and a halodialkylphosphine or halodiarylphosphine or haloalkylarylphosphine to produce a dialkylphosphinite or diarylphosphinite or alkylarylphosphinite of 2-hydroxy-2′,4′,6′-trialkyl-m-terphenyl respectively, each being of structure II in which E is O.

### Claim 36 (depends on 1, 35)

The process of claim 35 comprising the subsequent step of reacting the compound of structure II with a palladium halide so as to form a compound of structure I as defined in claim 1 in which E is O, m, n and n′ are all 2, n″ is 0 and both R groups are alkyl or both are aryl or one R is alkyl and the other is aryl.

### Claim 37 (depends on 1, 35)

The process of claim 35 comprising reacting the compound of structure II with a palladium halide in the presence of a phosphine ligand whereby the process forms a compound of structure I as defined in claim 1 in which E is O, m, n and n′ are all 1, n″ is 1 and both R groups are alkyl or both are aryl or one R is alkyl and the other is aryl and L is the phosphine ligand.

### Claim 38 (depends on 1, 36)

The process of claim 36 comprising the subsequent step of reacting the compound of structure I with a phosphine ligand, e.g. PCy3, so as to produce a compound of structure I as defined in claim 1 in which E is O, m, n and n′ are all 1, n″ is 1 and both R groups are alkyl or both are aryl or one R is alkyl and the other is aryl and L is the phosphine ligand, e.g. PCy3.

### Claim 39 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38)

The process of any one of claims 17 to 38 which is conducted as a one pot process without isolation of intermediates or in which any two or more contiguous steps are conducted as a one pot process.

### Claim 40 (depends on 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39)

The process of any one of claims 17 to 39 which is conducted as a continuous reaction or in which any one or more individual steps thereof is (are) conducted as a continuous reaction.

### Claim 41 (depends on 1)

A process for making a coupled compound comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate, with a compound V comprising an element M bonded directly to an alkyl, alkenyl, alkynyl, aryl or heteroaryl group, in which M is an element in one of groups 1, 2, 11, 12, 13 or 14, in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt or complex capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 42 (depends on 41)

The process of claim 41 wherein either Ra or compound V or both is substituted with one or more substituents.

### Claim 43 (depends on 42)

The process of claim 42 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl; halogen, ORb, NRbRc, BRbRc, SiRb3 or SiRbRc2 or SiRbRcRd, in which Rb, Rc and Rd are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 44 (depends on 43)

The process of claim 43 wherein compound V is a boronic acid.

### Claim 45 (depends on 1)

A process for making a olefinic compound comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with an olefin in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt or complex capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 46 (depends on 45)

The process of claim 45 wherein either Ra or the olefin or both is substituted with one or more substituents.

### Claim 47 (depends on 46)

The process of claim 46 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORb′, NRb′R″, BRbR″, SiRb3 or SiRbRc2 or SiRbRcRd, in which Rb, Rc and Rd are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl group.

### Claim 48 (depends on 1)

A process for making an alkynyl compound comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with a terminal alkyne in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 49 (depends on 48)

The process of claim 48 wherein Ra is substituted with one or more substituents.

### Claim 50 (depends on 49)

The process of claim 49 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORb, NRbRc, BRbRc, SiRb3 or SiRbRc2 or SiRbRcRd, in which Rb, Rc and Rd are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 51 (depends on 1)

A process for making an amine compound comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with a primary or secondary amine in the presence of either:
a compound of structure I as defined in claim 1 in which m= or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 52 (depends on 51)

The process of claim 51 wherein Ra is substituted with one or more substituents.

### Claim 53 (depends on 52)

The process of claim 52 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORb, NRbRc, BRbRc, SiRb3 or SiRbRc2 or SiRbRcRd, in which Rb, Rc and Rd are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 54 (depends on 51, 52, 53)

The process of any one of claims 51 to 53 wherein the amine is of the form ReNH2 or ReRfNH in which Re and Rf are, independently, alkyl, alkenyl, heteroaryl or aryl groups.

### Claim 55 (depends on 1)

A process for making an aryl carbonyl compound, e.g. a ketone or aldehyde or acid or ester, comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with carbon monoxide and a nucleophile M′-Nu, where Nu=OH, NR2, alkyl, aryl, SR, or ORa where each Ra is as described above, and M′ is H or a Group 1 or Group 2 (alkyl or alkaline earth) metal ion or is M″Rb, where M is Cu, Ag, Zn, AlR, GaRb, TlRb, CRb2, SiRb2, SnRb2, PbRb2, NRb or AsRb, where Rb is alkyl, alkenyl, alkynyl, aryl or heteroaryl, in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 56 (depends on 55)

The process of claim 55 wherein Ra is substituted with one or more substituents.

### Claim 57 (depends on 56)

The process of claim 56 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORc, NRcRd, BRcRd, SiRc3 or SiRcRd2 or SiRcRdRe, in which Rc, Rd and Re are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 58 (depends on 1)

A process for making a nitrile compound comprising reacting a compound of structure RaX in which R is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with a cyanide in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 59 (depends on 58)

The process of claim 58 wherein R is substituted with one or more substituents.

### Claim 60 (depends on 59)

The process of claim 59 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORc, NRcRd, BRcRd, SiRc3 or SiRcRd2 or SiRcRdRe, in which Rc, Rd and Re are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 61 (depends on 58, 59, 60)

The process of any one of claims 58 to 60 wherein the cyanide is a Group I metal cyanide or HCN.

### Claim 62 (depends on 1)

A process for making a phosphorus compound comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with a phosphorus reagent in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 63 (depends on 62)

The process of claim 62 wherein Ra is substituted with one or more substituents.

### Claim 64 (depends on 63)

The process of claim 63 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORc, NRcRd, BRcRd, SiRc3 or SiRcRd2 or SiRcRdRe, in which Rc, Rd and Re are each independently H, alkyl, alkenyl, alkynyl, OH, alkoxyl or aryl.

### Claim 65 (depends on 62, 63, 64)

The process of any one of claim 62 to 64 wherein the phosphorus reagent is X—PRb2 or X2—PRb where X═H or halide, or X2 is ═O or ═S or the phosphorus reagent is a protected phosphine such as a borane adduct.

### Claim 66 (depends on 1)

A process for making an ether comprising reacting a compound of structure RaX in which Ra is alkyl, alkenyl, alkynyl, aryl or heteroaryl and X is a leaving group such as halide or triflate with an alcohol in the presence of either:
a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd, or
a compound of structure I as defined in claim 1 in which m=0 and a palladium salt capable of reacting with the compound of structure I to form a compound of structure I in which m=1 or 2 and M=Pd.

### Claim 67 (depends on 66)

The process of claim 66 wherein Ra is substituted with one or more substituents.

### Claim 68 (depends on 67)

The process of claim 67 wherein each of the one or more substituents is, independently, alkyl, aryl, heteroaryl, halogen, ORc, NRcRd, BRcRd, SiRc3 or SiReRd2 or SiRcRdRe, in which Rc, Rd and Re are each independently H, alkyl, alkenyl, alkynyl, OH, amine, halogen, alkoxyl or aryl.

### Claim 69 (depends on 1)

Use of a compound of structure I as defined in claim 1 in which m=1 or 2 and M=Pd as a catalyst.

### Claim 70 (depends on 69)

Use according to claim 69, being for catalysis of a reaction selected from the group consisting of Suzuki-Miyaura, Kumada, Stille, Negishi and Hiyama coupling reactions, Heck and Sonogashira reactions, Buchwald-Hartwig amination, Heck carbonylation, alkoxylation, cyanation, phosphination and metal mediated coupling reactions.