Rhenium(V) alkylidyne complexes and methods of use and preparation thereof

Patent metadata

Field	Value
Publication number	US-11780864-B2
Application number	US-202217810660-A
Country	US
Kind code	B2
Filing date	Jul 5, 2022
Priority date	Jul 7, 2021
Publication date	Oct 10, 2023
Grant date	Oct 10, 2023

Abstract

Non-d 0 rhenium(V) alkylidyne catalysts useful for catalyzing alkyne metathesis reactions, such as homo- and cross-metathesis of alkynes or diynes, ring closing metathesis and ring-opening metathesis, methods or use, and preparation thereof. The catalysts are stable to air and moisture and tolerate a variety of functional groups in substrates.

First claim

What is claimed is:

1. A rhenium(V) alkylidyne complex of Formula 1:

wherein L is pyridine, 4-(trifluoromethyl)pyridine, nitrile, or PR 1 R 2 R 3 , wherein each of R 1 , R 2 , and R 3 is independently selected from the group consisting of alkyl and aryl;
R is alkyl, phenyl, 2-thiophene, or CH 2 Ar 1 , wherein Ar 1 is phenyl or o-bromophenyl;
each of R 4 and R 5 is independently phenyl optionally substituted with alkyl, CH 3 , OCH 3 , F or CF 3 ; and
R 6 for each instance is independently a moiety selected from the group consisting of

wherein * represents the site of the covalent bond to oxygen and ** represent the site of the covalent bond to phosphorous.

2. The rhenium(V) alkylidyne complex of claim 1 , wherein L is pyridine, PMePh 2 , or PMe 2 Ph.

3. The rhenium(V) alkylidyne complex of claim 1 , wherein R is CH 2 Ar 1 , wherein Ar 1 is phenyl or o-bromophenyl.

4. Cancelled) The rhenium(V) alkylidyne complex of claim 1 , wherein each of R 4 and R 5 is independently alkyl, cycloalkyl, or phenyl optionally substituted with one or more substituents selected from alkyl, CH 3 , OCH 3 , F, and CF 3 .

5. The rhenium(V) alkylidyne complex of claim 1 , wherein each of R 4 and R 5 is phenyl, 4-fluorophenyl, 2,4-difluorophenyl, 4-trifluoromethylphenyl, 2,4-bis(trifluoromethyl)phenyl, 2,4-dimethylphenyl, 4-methoxyphenyl, or 2,4-dimethoxyphenyl.

6. The rhenium(V) alkylidyne complex of claim 1 , wherein the rhenium(V) alkylidyne complex is selected from the group consisting of:

wherein R is alkyl, phenyl, 2-thiophene, or CH 2 Ar 1 , wherein Ar 1 is phenyl or o-bromophenyl; and L is pyridine, 4-(trifluoromethyl)pyridine, PMePb 2 , or PMe 2 Ph.

7. The rhenium(V) alkylidyne complex of claim 6 , wherein R is CH 2 Ph.

8. The rhenium(V) alkylidyne complex of claim 7 , wherein L is pyridine.

9. The rhenium(V) alkylidyne complex of claim 1 , wherein the rhenium(V) alkylidyne complex has the structure:

10. A method of preparing the rhenium (V) alkylidyne complex of claim 1 , the method comprising: contacting a compound of Formula 6:

wherein R is alkyl, phenyl, 2-thiophene, or CH 2 Ar 1 , wherein Ar 1 is phenyl or o-bromophenyl;
PR′ 3 is PMePh 2 or PMe 2 Ph;
each of R 4 and R 5 is independently phenyl optionally substituted with alkyl CH 3 , OCH 3 , F, or CF 3 ; and
R 6 for each instance is independently a moiety selected from the group consisting of:

wherein * represents the site of the covalent bond to oxygen and ** represent the site of the covalent bond to phosphorous;
with a compound of Formula 7:

wherein R 9 is hydrogen or CF 3 ; and a phosphine scavenger selected from CuCl or Cul; thereby forming the rhenium (V) alkylidyne complex of claim 1 .

11. The method of claim 10 , wherein the rhenium (V) alkylidyne complex is selected from the group consisting of:

wherein R is CH 2 Ph; and L is pyridine.

12. The method of claim 10 further comprising the step of contacting a compound of Formula 8:

wherein X 3 is Cl; PR; is PMePh 2 or PMe 2 Ph; R is alkyl, phenyl, 2-thiophene, or CH 2 Ar 1 , wherein Ar 1 is phenyl or o-bromophenyl; with a compound of Formula 9:

wherein each of R 4 and R 3 is independently phenyl optionally substituted with alkyl, CH 3 , OCH 3 , F, or CF 3 ; and R 6 is a moiety selected from the group consisting of:

wherein * represent the site of the covalent bond to oxygen and ** represents the site of the covalent bond to phosphorous thereby forming the compound of Formula 6.

13. The method of claim 12 , wherein the compound of Formula 8 has the structure:

14. The method of claim 12 , wherein the compound of Formula 9 is selected from the group consisting of: (2-hydroxyphenyl)diphenylphosphine, 2-bis(3,5-dimethyl phenyl)phosphinophenol, 2-[bis(4-methoxy phenyl)phosphino]phenol, [2-bis(4-fluorophenyl)phosphino]phenol, (2-hydroxyphenyl)-bis(2,4-difluorophenyl)phosphine, ), 2-{bis[4-(trifluoromethyl)phenyl]phosphino]}phenol, 2-{bis[3,5-bis(trifluoromethyl)phenyl]phosphino}phenol, and (2-hydroxy-5-trifluoromethylphenyl)diphenylphosphine.

15. A method for performing a metathesis reaction, the method comprising: contacting a rhenium(V) alkylidyne complex of claim 1 with at least one alkyne substrate thereby forming an alkyne metathesis product.

16. The method of claim 15 , wherein the metathesis reaction is an alkyne homo-metathesis reaction, alkyne cross-metathesis, ring closing alkyne metathesis, ring opening alkyne metathesis polymerization, acyclic diyne metathesis polymerization, or acyclic diyne metathesis macrocyclozation.

17. The method of claim 15 , wherein the alkylidyne complex is selected from the group consisting of:

wherein R is CH 2 Ph; and L is pyridine.

18. The method of claim 15 , wherein the at least one alkyne substrate is selected from the group consisting of an acyclic alkyne, a cyclic alkyne, an acyclic diyne, and a cyclic diyne.

Assignees

• Univ Hong Kong Science & Tech

Inventors

• Jia Guochen
• Cui Mingxu

Classifications

• C07F13/005 Primary

  Compounds without a metal-carbon linkage · CPC title

• B01J31/1616

  Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts (catalysts comprising molecular sieves B01J29/00) · CPC title

• C07F13/00 Primary

  Compounds containing elements of Groups 7 or 17 of the Periodic Table · CPC title

• B01J2231/546

  alkyne metathesis · CPC title

• B01J2531/74

  Rhenium · CPC title