Alternating current (AC) transition-metal catalysis

Patent metadata

Field	Value
Publication number	US-12392042-B2
Application number	US-202118043339-A
Country	US
Kind code	B2
Filing date	Sep 14, 2021
Priority date	Sep 15, 2020
Publication date	Aug 19, 2025
Grant date	Aug 19, 2025

Abstract

This invention provides a catalytic process wherein alternating current is used for catalytic coupling (such as C—C, C—N, C—O, C—S, C—P, C—Si and/or C—B couplings) using a transition-metal catalysis.

First claim

What is claimed is:

1. A catalytic coupling process, the process comprises reacting at least one functional group A with at least one functional group B in the presence of a transition metal as a catalyst under AC voltage; wherein the reaction between the functional group A and the functional group B is intermolecular or intramolecular resulting in a C—N, C—O, C—S, C—P, C—Si, C—B or combination thereof coupling product,
wherein the process is conducted in an electrochemical cell, wherein the cell comprises:
a first electrode, a second electrode and an electrolyte;

wherein the transition-metal catalyst is dissolved in said electrolyte; and
wherein by applying the AC voltage between said first electrode and said second electrode sequential oxidation and reduction of said transition metal occur and thereby inducing a coupling reaction between at least one functional group A and at least one functional group B.

2. The process of claim 1 , wherein the at least one functional group A is a functional group of a first compound and the at least one functional group B is a functional group of a second compound, and the coupling reaction is intermolecular.

3. The process of claim 2 , wherein the first compound comprises two or more functional groups A and the second compound comprises two or more functional groups B, and the coupling reaction will form a polymerized coupling product.

4. The process of claim 2 , wherein said first compound comprises at least one functional group A is an aromatic halide and the second compound comprises at least one functional group B is a nucleophile.

5. The process of claim 4 , wherein the nucleophile comprises R—OH, R—NH 2 , R—NH—R 1 , R—COOH, N 3 − , CN − , R—SH, R—C(O) NH—R 1 , R—PH—R 1 , (RO)—P(O) H—(OR 1 ), R—P(O) H—(OR 1 ), HSi—(R) 3 , HB—(OR) 2 , HB—(R) 2 (OR) 2 —B—B—(OR) 2 , wherein R is H, substituted or unsubstituted alky, aryl, heteroaryl, cycloalkyl or heterocycloalkyl; R 1 is H, substituted or unsubstituted alky, aryl, heteroaryl, cycloalkyl or heterocycloalkyl; or R and R 1 form together a cyclic 5-6 membered ring.

6. The process of claim 1 , wherein the functional group A and the functional group B is of a third compound, and the coupling product is intramolecular.

7. The process of claim 1 , wherein:
at least one oxidation process and at least one reduction process of said transition metal catalyst occur by electron transfer to or from said first electrode;
at least one oxidation process and at least one reduction process of said transition metal catalyst occur by electron transfer to or from said second electrode; or
a combination thereof.

8. The process of claim 1 , wherein the transition metal catalyst comprises Ni(II), Ru(II, III), Cu(I, II), Co(II, III), Fe(II, III), Cr(II, III, VI), V(II, III, IV, V), Ti(IV), Mo(III, IV, V, VI) or any combination thereof.

9. The process of claim 8 , wherein the transition metal catalyst is a complex comprising a transition metal and a ligand, wherein the ligand comprises nitrogen-based ligands, phosphorus-based ligands or combination thereof.

10. The process of claim 9 , wherein the nitrogen-based ligands comprise a bipyridyl group, di- t BuBipy, pyridine, 1,10-phenanthroline, 4,7-Diphenyl-1,10-phenanthroline or combination thereof, or wherein the phosphorus-based ligands comprise 1,2-Bis (diphenylphosphino) ethane (dppe), triphenylphosphine, tricyclohexylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) or combination thereof.

11. The process of claim 1 , wherein the C-N coupling comprises an amination reaction.

12. The process of claim 1 , wherein the C-O coupling comprises an esterification and etherification reactions.

13. The process of claim 1 , wherein the process is a catalytic process and comprises reductive elimination and oxidative addition of the transition metal intermediates within the catalytic cycle.

14. The process of claim 1 , wherein the concentration of the transition-metal in the electrolyte ranges between 0.1 to 20 mol % of catalyst vs. at least one functional group A, and at least one functional group B.

15. The process of claim 1 , wherein the electrolyte comprises an organic solvent.

16. The process of claim 15 , wherein the organic solvent is selected from the group consisting of dimethylformamide (DMF) and/or dimethylacetamide (DMA), and LiBr and/or NBu 4 PF 6 .

17. The process of claim 1 , wherein the first electrode and second electrode comprise glassy carbon rod, foam, plate or porous electrode, or wherein the first electrode and second electrode comprise carbon , Ag, Pt, Au, W, Pb, Ti, Ni, Co or stainless steel.

18. The process of claim 1 , wherein the frequency of the applied voltage ranges between 0.5 Hz and 100 Hz and the amplitude of the applied AC voltage is at least 1V, or wherein the yield of the process is at least 50%, or at least 60% or at least 75%, or at least 80%, or wherein the amount of side-products formed is less than 5%.

Assignees

• Yeda Res & Dev

Inventors

• Semenov Sergey N
• Bortnikov Evgenii

Classifications

• C25B3/03 Primary

  Acyclic or carbocyclic hydrocarbons · CPC title

• C25B3/09

  Nitrogen containing compounds · CPC title

• C25B3/07

  Oxygen containing compounds · CPC title

• B01J2231/4277

  C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues · CPC title

• B01J31/1805

  the ligands containing nitrogen · CPC title