Phosphorus-containing catalysts

Patent metadata

Field	Value
Publication number	US-2016207034-A1
Application number	US-201414913479-A
Country	US
Kind code	A1
Filing date	Aug 29, 2014
Priority date	Aug 29, 2013
Publication date	Jul 21, 2016
Grant date	—

Abstract

The invention provides compounds of general structure I: (Ar 1 —Ar 2 —Ar 3 -E-P(=D)R 2 -) n M m X n L n ″. In this structure: •Ar 1 , Ar 2 and Ar 3 are aromatic groups wherein: —Ar 1 and Ar 3 are in a 1,3 relationship on Ar 2 , —each of Ar 1 , Ar 2 and Ar 3 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, —Ar 1 , Ar 2 and Ar 3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar 1 , Ar 2 and Ar 3 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)CF 3 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.

First claim

1 . A compound of structure I:
(Ar 1 —Ar 2 —Ar 3 -E-P(=D)R 2 —-) n M m X n′ L n″

wherein:
Ar 1 , Ar 2 and Ar 3 are aromatic groups wherein:
Ar 1 and Ar 3 are in a 1,3 relationship on Ar 2 ,
each of Ar 1 , Ar 2 and Ar 3 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,
Ar 1 , Ar 2 and Ar 3 are each independently carbocyclic or heterocyclic and each is independently monocyclic, bicyclic or polycyclic and each ring of each of Ar 1 , Ar 2 and Ar 3 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)CF 3 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.

2 . The compound of claim 1 wherein m is 1 or 2 and M is bonded to a ring atom of Ar 3 ortho to E.

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

4 . 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.

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

6 . The compound of claim 5 wherein M is Pd.

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

8 . The compound of claim 1 wherein m=0.

9 . The compound of claim 1 wherein m=1.

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

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

12 . 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.

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

14 . 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.

15 . The compound of claim 1 wherein Ar 1 is phenyl, Ar 2 is 2,4,6-trimethylphenyl or 2,4,6-triisopropylphenyl, Ar 3 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.

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

17 . A process for making a compound of structure I as defined in claim 1 , said process comprising reacting a compound of structure II:
Ar 1 —Ar 2 —Ar 3 -E-PR 2
wherein Ar 1 , Ar 2 and Ar 3 , E and R are as defined in claim 1 and Ar 1 and Ar 3 are in a 1,3 relationship on Ar 2 , with a salt or complex of M, optionally in the presence of a liganding species.

18 . 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.

19 . 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.

20 . 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.

21 . 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) 2 Cl 2 , Pd(CN) 2 or Pd(MeCN) 4 (BF 4 ) 2 or Pd(COD)(CH 2 TMS) 2 or Pd(NBD)(CH 2 TMS) 2 ), or a halide or acetate or cyanide salt or a salt of a pseudohalide, e.g. triflate, of M.

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

23 . The process of claim 22 wherein M is Pd.

24 . The process of any one of claims 17 to 23 comprising reacting a compound of structure III:
Ar 1 —Ar 2 —Ar 3 -E-X

wherein Ar 1 , Ar 2 and Ar 3 and E are as defined in claim 1 and Ar 1 and Ar 3 are in a 1,3 relationship on Ar 2 ,
with either:
a compound of structure X—PR 2 , wherein R is as defined in claim 1 or
a compound of structure X—P(D)R 2 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)CF 3 and OAc
so as to produce the compound of structure II.

25 . A process for making a compound of structure II as defined in claim 17 comprising reacting a compound of structure III:
Ar 1 —Ar 1 —Ar 3 -E-X

wherein Ar 1 , Ar 2 and Ar 3 and E are as defined above and Ar 1 and Ar 3 are in a 1,3 relationship on Ar 2 ,
with either:
a compound of structure X—PR 2 , wherein R is as defined in claim 1 or
a compound of structure X—P(D)R 2 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)CF 3 and OAc.

26 . The process of any one of claims 17 to 25 wherein each ring in Ar 1 , Ar 2 and Ar 3 has independently, 5 or 6 ring carbon atoms.

27 . The process of any one of claims 17 to 26 wherein at least one of Ar 1 , Ar 2 and Ar 3 is a fused aromatic ring or a fused heteroaryl ring.

28 . The process of any one of claims 17 to 26 wherein each of Ar 1 , Ar 2 and Ar 3 is monocyclic, e.g. is a phenyl ring.

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

30 . 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.

31 . The process of

Assignees

• Agency Science Tech & Res

Inventors

• Johannes Charles W
• Robins Edward G
• Jong Howard
• Lim Yee Hwee
• Chia Saei Weng
• Yang Yong
• Podichetty Anil

Classifications

• B01J31/1875 Primary

  Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof) · CPC title

• C07F9/5063

  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) · CPC title

• C07D295/033

  with the ring nitrogen atoms directly attached to carbocyclic rings · CPC title

• C07D209/10

  with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title