Methods of arene alkenylation

Patent metadata

Field	Value
Publication number	US-12404221-B2
Application number	US-202117999273-A
Country	US
Kind code	B2
Filing date	May 19, 2021
Priority date	May 19, 2020
Publication date	Sep 2, 2025
Grant date	Sep 2, 2025

Abstract

The present disclosure provides for a rhodium-catalyzed oxidative arene alkenylation from arenes and styrenes to prepare stilbene and stilbene derivatives. For example, the present disclosure provides for method of making arenes or substituted arenes, in particular stilbene and stilbene derivatives, from a reaction of an optionally substituted arene and/or optionally substituted styrene. The reaction includes a Rh catalyst or Rh pre-catalyst material and an oxidant, where the Rh catalyst or Rh catalyst formed Rh pre-catalyst material selectively functionalizes CH bond on the arene compound (e.g., benzene or substituted benzene).

First claim

The invention claimed is:

1. A method of making a substituted arene, comprising:

wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the arene compound, wherein B is an oxidant, wherein the Rh catalyst is a composition comprising:
a rhodium (I) catalyst having one of the following formula: L 2 Rh(L′)X, L 3 RhX, (L 1 X 1 )Rh(L′), [(L) 2 Rh(μ-X)] 2 , RhX 3 , [L n Rh y (m-X) m ], or (L) n Rh m
wherein L 2 is selected from:
two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
a combination of the neutral first ligand and the neutral bidentate ligand;

wherein L′ is a neutral second ligand coordinated to Rh(I),
wherein X is a mono-anionic group, either coordinated to the metal or not,
wherein L 3 is a tridentate first ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L 1 X 1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
wherein y is 1 to 4, m is 1 to 4 and n is 3(m).

2. The method of claim 1 , wherein the oxidant is selected from the group consisting of a copper(II) salt, iodates, periodates, nitrogen oxide, silver salt, peroxide, dioxygen, copper(I) salt and one or both of dioxygen and air, and a combination thereof.

3. The method of claim 1 , wherein the Rh pre-catalyst material comprises Rh nanoparticles on a support or single atom Rh material on the support.

4. The method of claim 1 , wherein the ratio of the benzene to styrene is about 1:100 to 1000:1, wherein the amount of Rh catalyst is about 20 mol % to 0.000000001 mol %, wherein the amount of oxidant is about 2 to 10,000 equivalents relative to Rh catalyst.

5. The method of claim 1 , wherein the reaction temperature is about 125-205° C. for about 1 to 72 hours.

6. A method of making a substituted arene, comprising:

wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes CH bond on the benzene compound, wherein B is an oxidant, wherein R51 to R58 are each independently selected from the group consisting of: hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO 2 , —C(O)OR′, —CN, SiR′ 3 , and —OR′, wherein each R′ is independently selected from H and an alkyl, wherein the Rh catalyst is a composition comprising:
a rhodium (I) catalyst having one of the following formula: L 2 Rh(L′)X, L 3 RhX, (L 1 X 1 )Rh(L′), [(L) 2 Rh(μ-X)] 2 , RhX 3 , [L n Rh y (m-X) m ], or (L) n Rh m
wherein L 2 is selected from:
two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
a combination of the neutral first ligand and the neutral bidentate ligand;

wherein L′ is a neutral second ligand coordinated to Rh(I),
wherein X is a mono-anionic group, either coordinated to the metal or not,
wherein L 3 is a tridentate first ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L 1 X 1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
wherein y is 1 to 4, m is 1 to 4 and n is 3(m).

7. The method of claim 6 , wherein the oxidant is selected from the group consisting of a copper(II) salt, iodates, periodates, nitrogen dioxide, silver salt, peroxide, dioxygen, copper(I) salt and one or both of dioxygen and air, and a combination thereof.

8. The method of claim 6 , wherein the Rh pre-catalyst material comprises a Rh nanoparticles on a support or single atom Rh material on the support.

9. The method of claim 6 , wherein the ratio of the benzene to styrene is about 1:100 to 1000:1, wherein the amount of Rh catalyst is about 20 mol % to 0.000000001 mol %, wherein the amount of oxidant is about 2 to 10,000 equivalents relative to Rh catalyst.

10. The method of claim 6 , wherein the reaction temperature is about 125-205° C. for about 2 to 72 hours.

11. A method of making a substituted arene, comprising:

wherein A is a Rh catalyst or Rh pre-catalyst material, wherein the Rh catalyst selectively functionalizes a CH bond in meta and para positions of the substituted benezene relative to the functional group, wherein B is an oxidant,
wherein R51 to R58 are each independently selected from the group consisting of: hydrogen, a halide, an alkyl, an alkenyl, a —O—R′, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO 2 , —C(O)OR′, —CN, SiR′ 3 , and —OR′, wherein each R′ is independently selected from H and an alkyl,
wherein R61 to R66 are each independently selected from the group consisting of: hydrogen, a halide, an alkyl, an alkenyl, a —O—R″, a carbocycle group, a heterocyclo, an aryl, a heteroaryl, —NO 2 , —C(O)OR″, —CN, SiR″ 3 and —OR″, wherein each R″ is independently selected from H and an alkyl,
wherein the Rh catalyst is a composition comprising:
a rhodium (I) catalyst having one of the following formula: L 2 Rh(L′)X, L 3 RhX, (L 1 X 1 )Rh(L′), [(L) 2 Rh(μ-X)] 2 , RhX 3 , [L n Rh y (m-X) m ], or (L) n Rh m
wherein L 2 is selected from:
two independent and neutral first ligands each coordinated to Rh(I) through a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor,
a neutral bidentate ligand coordinated to Rh(I) through either a carbon donor, nitrogen donor, a phosphorus donor, an oxygen donor, or a sulfur donor, or
a combination of the neutral first ligand and the neutral bidentate ligand;

wherein L′ is a neutral second ligand coordinated to Rh(I),
wherein X is a mono-anionic group, either coordinated to the metal or not,
wherein L 3 is a tridentate first ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L 1 X 1 is a monoanionic bidentate or tridentate second ligand coordinated to Rh(I) in a κ 2 or κ 3 fashion through a carbon donor, a nitrogen donor, a phosphorus donor, an oxygen donor, a sulfur donor, or a combination thereof,
wherein L is a neutral, two-electron donating third ligand coordinated to Rh(I), and
wherein y is 1 to 4, m is 1 to 4 and n is 3(m).

Assignees

• Univ Virginia Patent Foundation

Inventors

• Gunnoe Thomas Brent
• Jia Xiaofan
• Frye Lucas Isaac

Classifications

• C07D307/36

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

• C07C2523/46

  Ruthenium, rhodium, osmium or iridium · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07C201/12

  by reactions not involving the formation of nitro groups · CPC title

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title