Complexes

Patent metadata

Field	Value
Publication number	US-9777030-B2
Application number	US-201515317725-A
Country	US
Kind code	B2
Filing date	Mar 20, 2015
Priority date	Jun 12, 2014
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A palladium(II) complex of formula (1) or a palladium(II) complex of formula (3).

Also, processes for the preparation of the complexes, and their use in carbon-carbon and carbon-heteroatom coupling reactions.

First claim

The invention claimed is:

1. A palladium(II) complex of formula (1):

wherein:
Pd ⊕ is a cationic palladium atom;
R 1 and R 2 are, independently, an organic group having 1-20 carbon atoms, or R 1 and R 2 are linked to form a ring structure with E;
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are, independently, —H or an organic group having 1-20 carbon atoms; or
R 1 /R 3 or R 2 /R 3 forms a ring structure with the atoms to which they are attached and in this instance R 4 /R 5 , R 5 /R 6 , R 7 /R 8 , R 8 /R 9 , R 9 /R 10 or R 10 /R 11 , independently, form a ring structure with the carbon atoms to which they are attached or R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are as defined above;
R 12 is an organic group having 1-20 carbon atoms;
m is 0, 1, 2, 3, 4 or 5;
E is P or As; and
X ⊖ is a non-coordinated anionic ligand.

2. A palladium(II) complex according to claim 1 , wherein E is P.

3. A palladium(II) complex according to claim 1 , wherein R 1 and R 2 are, independently, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl wherein the heteroatoms of the substituted or unsubstituted heteroaryl are, independently, sulfur, nitrogen or oxygen.

4. A palladium(II) complex according to claim 1 , wherein R 3 , R 4 , R 5 and R 6 are, independently, —H, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted —N(alkyl) 2 (wherein the alkyl is the same or different and is, independently, a straight-chain or branched-chain alkyl), substituted or unsubstituted —N(cycloalkyl) 2 (wherein the cycloalkyl is the same or different), substituted or unsubstituted —N(aryl) 2 (wherein the aryl is the same or different), substituted or unsubstituted —N(heteroaryl) 2 (wherein the heteroaryl is the same or different) or substituted or unsubstituted heterocycloalkyl.

5. A palladium(II) complex according to claim 4 , wherein R 3 , R 4 , R 5 and R 6 are —H.

6. A palladium(II) complex according to claim 4 , wherein R 3 , R 4 , R 5 and R 6 are, independently, a straight-chain alkyl.

7. A palladium(II) complex according to claim 1 , wherein two of R 3 , R 4 , R 5 and R 6 are —H, and the other two of R 3 , R 4 , R 5 and R 6 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, or unsubstituted alkoxy.

8. A palladium(II) complex according to claim 1 , wherein R 7 , R 8 , R 9 , R 10 and R 11 are, independently, —H, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted —N(alkyl) 2 (wherein the alkyl is the same or different and is, independently, a straight-chain or branched-chain alkyl), substituted or unsubstituted —N(cycloalkyl) 2 (wherein the cycloalkyl is the same or different), substituted or unsubstituted —N(aryl) 2 (wherein the aryl is the same or different), substituted or unsubstituted —N(heteroaryl) 2 (wherein the heteroaryl is the same or different) or substituted or unsubstituted heterocycloalkyl.

9. A palladium(II) complex according to claim 7 , wherein R 7 , R 8 , R 9 , R 10 and R 11 are —H.

10. A palladium(II) complex according to claim 7 , wherein three of R 7 , R 8 , R 9 , R 10 and R 11 are —H, and the other two of R 7 , R 8 , R 9 , R 10 and R 11 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, unsubstituted alkoxy, unsubstituted —N(alkyl) 2 (wherein the alkyl is the same or different and, independently, straight-chain or branched-chain alkyl), or unsubstituted —N(aryl) 2 (wherein the aryl is the same or different).

11. A palladium(II) complex according to claim 7 , wherein two of R 7 , R 8 , R 9 , R 10 and R 11 are —H, and the other three of R 7 , R 8 , R 9 , R 10 and R 11 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, unsubstituted alkoxy, unsubstituted —N(alkyl) 2 (wherein the alkyl is the same or different and, independently, straight-chain or branched-chain alkyl) or unsubstituted —N(aryl) 2 (wherein the aryl is the same or different).

12. A palladium(II) complex according to claim 1 , wherein the

moiety is a monodentate tertiary phosphine ligand that is:

13. A palladium(II) complex according to claim 1 , wherein each R 12 is, independently, substituted or unsubstituted straight-chain alkyl, substituted or unsubstituted branched-chain alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl wherein the heteroatoms of the heteroaryl are, independently, sulfur, nitrogen or oxygen.

14. A palladium(II) complex according to claim 1 , wherein X ⊕ is triflate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, [B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ] − or mesylate.

15. A palladium(II) complex according to claim 1 , wherein the complex of formula (1) is:

16. A palladium(II) complex of formula (3):

wherein:
R 1 and R 2 are, independently, an organic group having 1-20 carbon atoms, or R 1 and R 2 are linked to form a ring structure with E;
R 12 is an organic group having 1-20 carbon atoms;
R 20 , R 21 , R 22 , R 23 and R 24 are, independently, —H or an organic group having 1-20 carbon atoms; or
one or more pairs of R 1 /R 20 , R 2 /R 20 , R 20 /R 21 or R 22 /R 23 , independently, form a ring structure with the atoms to which they are attached;
m is 0, 1, 2, 3, 4 or 5; and

Assignees

• Johnson Matthey Plc

Inventors

• Colacot Thomas
• Jon Deangelis Andrew

Classifications

• C07F15/006 Primary

  Palladium compounds · CPC title

• C07D263/22

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms · CPC title

• C07D213/76

  to which a second hetero atom is attached (nitro radicals C07D213/61) · CPC title

• B01J31/2419

  comprising P as ring member · CPC title

• B01J2231/4205

  C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type · CPC title