Phosphine triply cross-linked by organic polymer, transition metal complex using said phosphine as a ligand, and catalyst

Patent metadata

Field	Value
Publication number	US-10010879-B2
Application number	US-201414772424-A
Country	US
Kind code	B2
Filing date	Mar 6, 2014
Priority date	Mar 7, 2013
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

Provided are: a polymer-supported phosphane compound exhibiting excellent catalytic reaction activity; a complex including the compound and a transition metal; and a catalyst including the complex. This polymer compound includes: units of threefold styrene cross-linked phosphane; and styrene units having substituent groups (R) in position 4 (provided that R represents hydrogen, a C1-6 lower alkyl group, a C1-6 lower alkoxy group, or a polar functional group). In the formula in which the polymer compound includes structure (1), PS represents a polystyrene unit chain including the styrene units having the substituent groups (R). The complex includes the polymer and a transition metal. The catalyst for an organic compound coupling reaction includes the complex.

First claim

What is claimed is:

1. A complex comprising a polymer compound and a transition metal, wherein the polymer compound comprises a threefold styrene cross-linked phosphane unit and styrene units each having a substituent R at the 4-position, wherein R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, or a polar functional group, wherein the styrene units have substituents R which are the same or different, and wherein the polymer compound binds to the transition metal only through a phosphine group in the threefold styrene cross-linked phosphane unit.

2. The complex according to claim 1 , further comprising, as a ligand, an atom or group selected from halogen, carbonyl, hydroxy, nitro, amino, sulfonyl, and cyano.

3. The complex according to claim 2 , wherein when the ligand is carbonyl, the carbonyl is present in a group selected from ester, aldehyde, ketone, and amide.

4. The complex according to claim 1 , wherein the transition metal is selected from palladium, iridium, rhodium, platinum, ruthenium, nickel, and copper.

5. The complex according to claim 1 , comprising a structure (1) below:

wherein PS represents a polystyrene unit chain composed of the styrene units each having the substituent R.

6. The complex according to claim 1 , wherein the polymer compound is a copolymer of a tris(4-vinylphenyl)phosphane unit and the styrene units each having a substituent R, wherein the substituents R are the same or different, and when the substituents R are different, the styrene units having different substituents R are contained in the polymer compound with random arrangement.

7. The complex according to claim 6 , wherein an equivalence ratio of the tris(4-vinylphenyl)phosphane unit and the styrene units each having a substituent R falls in a range of 1:(20 to 1000).

8. The complex according to claim 7 , wherein the copolymer further contains crosslinkage through a divinylbenzene unit.

9. The complex according to claim 8 , wherein the equivalence ratio of the tris(4-vinylphenyl)phosphane unit, the styrene units each having a substituent R and the divinylbenzene unit falls in a range of 1:(20 to 1000):(0.1 to 20).

10. The complex according to claim 1 , wherein the polymer compound exhibits a swelling volume in toluene or cyclopentyl methyl ether of 2.0 to 7.0 mL/g.

11. The complex according to claim 1 , wherein the polar functional group is selected from a hydroxy group, a polyether group, an acetoxy group, an ester group, and an amide group.

12. The complex according to claim 1 , wherein the polymer compound contains no metal.

13. A method of preparation of a complex, the method comprising reacting a polymer compound and a transition metal comprising compound to obtain a complex, wherein the polymer compound comprises a threefold styrene cross-linked phosphane unit and styrene units each having a substituent R at the 4-position, wherein R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, or a polar functional group, wherein the styrene units have substituents R which are the same or different, and wherein the polymer compound binds to the transition metal only through a phosphine group in the threefold styrene cross-linked phosphane unit.

14. The method according to claim 13 , comprising a structure (1) below:

wherein PS represents a polystyrene unit chain composed of the styrene units each having the substituent R.

15. The method according to claim 13 , wherein the polymer compound is a copolymer of a tris(4-vinylphenyl)phosphane unit and the styrene units each having a substituent R, wherein the substituents R are the same or different, and when the substituents R are different, the styrene units having different substituents R are contained in the polymer compound with random arrangement.

16. The method according to claim 15 , wherein an equivalence ratio of the tris(4-vinylphenyl)phosphane unit and the styrene units each having a substituent R falls in a range of 1:(20 to 1000).

17. The method according to claim 15 , wherein the copolymer further contains crosslinkage through a divinylbenzene unit.

18. The method according to claim 17 , wherein the equivalence ratio of the tris(4-vinylphenyl)phosphane unit, the styrene units each having a substituent R and the divinylbenzene unit falls in a range of 1:(20 to 1000):(0.1 to 20).

19. The method according to claim 13 , wherein the polymer compound exhibits a swelling volume in toluene or cyclopentyl methyl ether of 2.0 to 7.0 mL/g.

20. The method according to claim 13 , wherein the polar functional group is selected from a hydroxy group, a polyether group, an acetoxy group, an ester group, and an amide group.

21. The method according to claim 13 , wherein the polymer compound contains no metal.

22. A method of carrying out a coupling reaction of organic compounds, the method comprising performing the coupling reaction in the presence of a catalyst, wherein the catalyst comprises the complex according to claim 1 .

23. The method according to claim 22 , wherein the coupling reaction is selected from a C—C coupling reaction, a C—N coupling reaction, and a C(sp 3 )-H borylation.

Assignees

• Univ Hokkaido Nat Univ Corp
• Tosoh Organic Chemical Co Ltd

Inventors

• Sawamura Masaya
• Iwai Tomohiro
• Harada Tomoya

Classifications

• C08F230/02

  containing phosphorus · CPC title

• C08F212/14

  substituted by heteroatoms or groups containing heteroatoms · CPC title

• C08F12/14

  substituted by hetero atoms or groups containing heteroatoms · CPC title

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title

• C07C2531/24

  Phosphines · CPC title