Acyclic carbene ligand for ruthenium complex formation, ruthenium complex catalyst, and use thereof

Patent metadata

Field	Value
Publication number	US-11559797-B2
Application number	US-202017091669-A
Country	US
Kind code	B2
Filing date	Nov 6, 2020
Priority date	Nov 8, 2019
Publication date	Jan 24, 2023
Grant date	Jan 24, 2023

Abstract

Provided are a novel acyclic carbene ligand for ruthenium complex formation; a ruthenium complex catalyst using the ligand; a method of using the complex as a catalyst in an ethylene-metathesis ethenolysis reaction; a method of preparing the ruthenium complex catalyst; and a method of preparing a linear alpha-olefin, the method including the step of reacting a linear or cyclic alkene compound in the presence of the ruthenium complex catalyst.The acyclic carbene ligand of the present invention and the ruthenium complex catalyst using the same have high selectivity and turnover number for terminal olefin formation in an ethylene-metathesis ethenolysis reaction, and thus linear α-olefins may be prepared with a high yield.

First claim

What is claimed is:

1. An acyclic carbene ligand for the formation of a ruthenium complex, the acyclic carbene ligand having a structure of Chemical Formula 2:

wherein, in Chemical Formula 2,
n is an integer of 0 to 4,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group, and
R 5 is a hydrogen atom or C 1 -C 6 alkyl group.

2. The acyclic carbene ligand of claim 1 , wherein n is an integer of 1 or 2, and R 3 and R 4 are each independently propyl, butyl, or diphenylmethyl.

3. A ruthenium complex catalyst having a structure of Chemical Formula 3:

wherein, in Chemical Formula 3,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group; or R 1 and R 2 are connected to each other to form an unsubstituted or substituted 4- to 8-membered heterocycle with a nitrogen atom to which they are connected,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group,
R 5 is a hydrogen atom or C 1 -C 6 alkyl group,
R 6 and R 7 are each independently a halogen,
R 8 is a substituted or unsubstituted C 1 -C 10 alkyl group, C 5 -C 10 carbocycle, or 5- to 10-membered heterocycle,
R 9 and R 10 are each independently a C 1 -C 10 alkyl group, or are connected to each other to form a C 5 -C 10 carbocycle or a 5- to 10-membered heterocycle, and
R 11 is N or O.

4. The ruthenium complex catalyst of claim 3 , wherein the ruthenium complex catalyst has a structure of the following Chemical Formula 4:

wherein, in Chemical Formula 4,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group; or R 1 and R 2 are connected to each other to form an unsubstituted or substituted 4- to 8-membered heterocycle with a nitrogen atom to which they are connected,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group,
R 5 is a hydrogen atom or C 1 -C 6 alkyl group, and
R 8 is a substituted or unsubstituted C 1 -C 10 alkyl group, C 5 -C 10 carbocycle, or 5- to 10-membered heterocycle.

5. The ruthenium complex catalyst of claim 4 , wherein the ruthenium complex catalyst has a structure of Chemical Formula 5:

wherein, in Chemical Formula 5,
n is an integer of 0 to 4,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group,
R 5 is a hydrogen atom or C 1 -C 6 alkyl group, and
R 8 is a substituted or unsubstituted C 1 -C 10 alkyl group, C 5 -C 10 carbocycle, or 5- to 10-membered heterocycle.

6. The ruthenium complex catalyst of claim 5 , wherein n is an integer of 1 or 2, and
R 3 and R 4 are each independently propyl, butyl, or diphenylmethyl.

7. A method of using the ruthenium complex of claim 3 as a catalyst in an ethylene-metathesis ethenolysis reaction of a linear or cyclic alkene compound.

8. A method of preparing a ruthenium complex catalyst, the method comprising the steps of:
treating formamide with oxalyl chloride to obtain an intermediate;
reacting the intermediate with alkoxysilane to obtain an acyclic carbene ligand having a structure of Chemical Formula 1; and
binding the ligand with ruthenium to form a ruthenium complex catalyst having a structure of Chemical Formula 4:

wherein, in the above Chemical Formulae,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group; or R 1 and R 2 are connected to each other to form an unsubstituted or substituted 4- to 8-membered heterocycle with a nitrogen atom to which they are connected,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group,
R 5 is a hydrogen atom or C 1 -C 6 alkyl group, and
R 8 is a substituted or unsubstituted C 1 -C 10 alkyl group, C 5 -C 10 carbocycle, or 5- to 10-membered heterocycle.

9. The method of claim 8 , wherein the step of obtaining the ligand is a step of obtaining an acyclic carbene ligand having a structure of Chemical Formula 2, and the step of forming the ruthenium complex catalyst is a step of forming a ruthenium complex catalyst having a structure of Chemical Formula 5:

wherein, in the above Chemical Formulae,
n is an integer of 0 to 4,
R 3 and R 4 are each independently a hydrogen atom, a substituted or unsubstituted C 1 -C 6 alkyl group, C 1 -C 6 alkenyl group, C 1 -C 6 alkynyl group, C 3 -C 8 cycloalkyl group, or C 6 -C 10 aryl group,
R 5 is a hydrogen atom or C 1 -C 6 alkyl group, and
R 8 is a substituted or unsubstituted C 1 -C 10 alkyl, C 5 -C 10 carbocycle, or 5- to 10-membered heterocycle.

10. The method of claim 8 , wherein the step of binding the ligand with ruthenium to form a ruthenium complex catalyst is a step of forming a ruthenium complex catalyst via a phosphine exchange reaction with a phosphine ruthenium catalyst.

11. A method of preparing linear alpha-olefins, the method comprising the step of reacting a linear or cyclic alkene compound in the presence of the ruthenium complex catalyst of claim 3 .

Assignees

• Gwangju Inst Science & Tech

Inventors

• Hong Sukwon
• Byun Seunghwan

Classifications

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J2531/004

  Ligands · CPC title

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title

• C07D207/20 Primary

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms · CPC title

• B01J2231/48

  Ring-opening reactions · CPC title