Ruthenium-based metathesis catalysts, precursors for their preparation and their use

Patent metadata

Field	Value
Publication number	US-11918985-B2
Application number	US-202318093009-A
Country	US
Kind code	B2
Filing date	Jan 4, 2023
Priority date	Oct 29, 2012
Publication date	Mar 5, 2024
Grant date	Mar 5, 2024

Abstract

The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost-effective manner.The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.

First claim

The invention claimed is:

1. An olefin metathesis reaction which comprises utilizing a ruthenium-based catalyst of formula (II)

wherein
wherein L is a N-heterocyclic carbene (NHC) ligand or

wherein L is a phosphine ligand selected from the group consisting of tri-isopropylphosphine, tricyclohexylphosphine (PCy 3 ), tricyclopentylphosphine, and phospha-bicycloalkane compounds selected from the group consisting of 9-cyclohexyl-9-phospha-bicyclo-[3.3.1]-nonane (“cyclohexylphobane”), 9-(2,2,4-trimethylpentyl)-9-phospha-bicyclo-[3.3.1]-nonane (“2,2 4-trimethylpentyl phobane”) and 9-isobutyl-9-phospha-bicyclo-[3.3.1]-nonane (“isobutylphobane”),
a, b, c and d are, independently from each other, selected from hydrogen, straight chain or branched C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, optionally substituted C 6 -C 14 -aryl, optionally substituted C 6 -C 14 -aryloxy, or optionally substituted C 6 -C 14 -heteroaryl;
R 1 is a straight chain or branched alkyl group including C 1 -C 10 -alkoxy, C 1 -C 10 -alkylthio, C 1 -C 10 -silyloxy, C 1 -C 10 -alkylamino, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -heterocyclic or electron-withdrawing groups (EWG);
X is an anionic ligand independently selected from the group of halogen anions (Cl − , Br − , I − ), tetrafluoroborate (BF 4 − ) or acetate (CH 3 COO − ),

wherein the electron-withdrawing groups are halogen atoms, trifluoromethyl (—CF 3 ), nitro (—NO 2 ), sulfinyl (—SO—), sulfonyl (—SO 2 —), formyl (—CHO), C 1 -C 10 -carbonyl, C 1 -C 10 -carboxyl, C 1 -C 10 -alkylamido, C 1 -C 10 -aminocarbonyl, nitrile (—CN) or C 1 -C 10 -sulfonamide.

2. The metathesis reaction as claimed in claim 1 , wherein the reaction is a ring-closing metathesis (RCM), cross metathesis (CM) or ring-opening metathesis polymerization (ROMP).

3. The metathesis reaction as claimed in claim 1 , wherein the olefin metathesis is carried out at temperatures <55° C. with catalyst loadings <0.1 mol-%.

4. The metathesis reaction as claimed in claim 1 , wherein reaction is a ring-closing metathesis (RCM), wherein the activity of the catalyst in the reaction (turn-over frequency, TOF) is >1×10 4 h −1 .

5. The metathesis reaction as claimed in claim 1 , wherein the ruthenium based catalyst is a catalyst of formula (IIa)

6. The metathesis reaction as claimed in claim 1 , wherein the ruthenium based catalyst is a catalyst of formula (IId)

7. The metathesis reaction as claimed in claim 1 , wherein the ruthenium-based catalyst is a catalyst of formula (IIe)

8. The metathesis reaction as claimed in claim 1 , wherein the ruthenium based catalyst is a catalyst of formula (IIh)

Assignees

• Umicore Ag & Co Kg

Inventors

• Plenio Herbert
• Kos Pavlo
• Savka Roman

Classifications

• B01J31/2208 Primary

  Oxygen, e.g. acetylacetonates · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J31/2278 Primary

  Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts · CPC title

• C07C5/31

  changing the number of rings · CPC title

• C07C43/275

  having all ether-oxygen atoms bound to carbon atoms of six-membered aromatic rings · CPC title