Method for aerobic oxidative coupling of thiophenes with a ligand-supported palladium catalyst

Patent metadata

Field	Value
Publication number	US-11773074-B2
Application number	US-202017087926-A
Country	US
Kind code	B2
Filing date	Nov 3, 2020
Priority date	Jan 9, 2018
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

An oxidative homocoupling method of synthesizing certain 2,2′-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions:

Associated catalytic systems and compositions are also disclosed.

First claim

We claim:

1. A catalytic system for catalyzing the synthesis of a 2,2′-bithiophene from two thiophenes, comprising:
oxygen gas;
palladium;
a transition metal, alkali metal, alkaline earth metal, bismuth salt, or aluminum salt; and
a ligand, wherein the ligand is selected from the group consisting of a 1,10-phenanthroline-5,6-dione, a 2,2′-bipyridine, a 2,2′-bipyrimidine, a 4,5-diazafluoren-9-one, a quinoline, a 1,10-phenanthroline, a bis(arylimino)acenaphthene, and a 2,2′-biquinoline.

2. The catalytic system of claim 1 , wherein the ligand is a 1,10-phenanthroline-5,6-dione having the chemical formula:

3. The catalytic system of claim 2 , wherein 1, 2, 3, 4, or 5 of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen, or wherein all 6 or R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen (the ligand is 1, 10-phenanthroline-5, 6-dione (phd)).

4. The catalytic system of claim 1 , wherein the ligand is a 2,2′-bipyridine having the chemical formula:

5. The catalytic system of claim 4 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from the group consisting of hydrogen, tert-butyl, methoxy, methyl, phenyl, and trifluoromethyl.

6. The catalytic system of claim 1 , wherein the ligand is a 2,2′-bipyrimidine having the chemical formula:

7. The catalytic system of claim 6 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is hydrogen.

8. The catalytic system of claim 1 , wherein the ligand is a 4,5-diazafluoren-9-one having the chemical formula:

9. The catalytic system of claim 8 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is hydrogen.

10. The catalytic system of claim 1 , wherein the ligand is a quinoline having the chemical formula:

11. The catalytic system of claim 10 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen.

12. The catalytic system of claim 1 , wherein the ligand is a 1,10-phenanthroline having the chemical formula:

13. The catalytic system of claim 12 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 R 7 , and R 8 is independently selected from the group consisting of hydrogen, methyl, and phenyl.

14. The catalytic system of claim 1 , wherein the ligand is a bis(arylimino)acenaphthene having the chemical formula:

15. The catalytic system of claim 14 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is hydrogen, or wherein one or both of Ar 1 and Ar 2 are selected from the group consisting of 4-methylphenyl and 1, 3, 4-trimethylphenyl.

16. The catalytic system of claim 1 , wherein the ligand is a 2,2′-biquinoline having the chemical formula:

17. The catalytic system of claim 16 , wherein one or more of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is hydrogen.

Assignees

• Wisconsin Alumni Res Found

Inventors

• Stahl Shannon
• Tereniak Stephen

Classifications

• C07D333/22 Primary

  Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• B01J31/181

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine · CPC title

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• B01J31/184

  mixed aromatic/aliphatic ring systems, e.g. indoline · CPC title