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Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone

A carbocyclic and allyl-based technology, applied in organic chemistry, ruthenium organic compounds, platinum group organic compounds, etc., can solve problems such as limited service life

Active Publication Date: 2011-06-01
MATERIA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the ruthenium NHC complex is significantly more stable than the corresponding bisphosphine complex, it has a limited lifetime

Method used

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  • Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone
  • Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone
  • Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone

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Experimental program
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Effect test

preparation example Construction

[0067] 2. Imidazoline salt preparation

[0068] Four-substituted or three-substituted imidazolines of formula (I) for forming the ruthenium catalyst of the present invention Salt NHC ligand precursors can be prepared from diamine derivatives bearing desired substituents and substitution patterns, as shown in the following examples. Typically, the diamine is dissolved in diethyl ether and treated with hydrogen chloride solution to precipitate the diamine hydrochloride. Diamine hydrochloride reacts with a large excess of triethyl orthoformate to give the desired imidazoline chloride of formula (I) Salt NHC ligand precursor. Alternatively, the diamine compound can also form a salt with trifluoroacetic acid or tetrafluoroboric acid, which likewise reacts with a large excess of triethylorthoformate to give the desired imidazoline of formula (I) Salt NHC ligand precursor.

[0069] 3. N-heterocyclic carbene (NHC) ruthenium catalyst of the present invention

[0070] The pres...

Embodiment 1

[0108] The preparation of embodiment 1.NHC ligand precursor (S):

[0109] Procedure A: A solution of the desired diamine in diethyl ether was treated with a solution of hydrogen chloride (2 equiv) to precipitate the diamine hydrochloride. The white solid was collected by filtration and washed with copious amounts of ether. The solid was placed in a flask and triethylorthoformate (large excess) was added. The resulting mixture was stirred at 130°C for 5 to 10 minutes and then cooled. After cooling to room temperature, the white solid was collected by filtration, washed with copious amounts of diethyl ether and then acetone to give the desired imidazoline chloride Salt S.

[0110] Procedure B: (see Jazzar, R.; Bourg, J.-B.; Dewhurst, R.D.; Donnadieu, B.; Bertrand, G.J.Org.Chem. 2007, 72, 3492-3499) The solution in hexane was added to a THF solution (40 mL) of the corresponding formamidine (1 equiv) at -78 °C. The mixture was stirred for 30 minutes, then allowed to warm to ...

Embodiment 1a

[0112] Example 1a.1,3-two yl-4-methyl-imidazoline chloride (S1) was prepared according to procedure B.

[0113]

[0114] 1 HNMR (500MHz, CDCl 3 ): δ9.70(s, 1H), 6.88(m, 4H), 5.02(m, 1H), 4.75(pseudo-t, J=11.5Hz, 1H), 3.85(dd, J=8.5Hz, J= 12.0Hz, 1H), 2.40-2.10(m, 18H), 1.50(d, J=6.5Hz, 3H). 13 CNMR (75MHz, CDCl 3 ): δ159.8, 140.4, 140.2, 135.8, 135.3, 135.1, 134.8, 130.4, 130.3, 130.2, 130.1, 130.0 (br s), 128.8, 60.5, 58.3, 21.1, 21.0, 19.0, 18.8, 18.5, 18.0 ( br s).

[0115] C 22 h 29 N 2 Calculated value of HRMS: 321.2331. Measured value: 321.2321.

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Abstract

This invention relates generally to olefin metathesis, more particularly, to tri- or tetra-substituted imidazolinium salts which are precursors to N-heterocyclic carbene (NHC) ligands with tri- or tetra-substituted irnidazolinium rings, organometallic ruthenium complexes comprising gem di-substituted imidazoiinium NHC ligands, organometallic ruthenium complexes comprising tri- or tetra-substituted imidazoiinium NHC ligands, and to olefin metathesis methods using them. The catalysts and methods of the invention have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

Description

[0001] governmental support [0002] This invention was supported by the National Institutes of Health under grant number GM031332. The US Government has certain rights in this invention. [0003] Cross References to Related Applications [0004] This application claims priority under 35 U.S.C. §119 to U.S. Provisional Application Serial No. 61 / 181,171, filed November 26, 2008, and U.S. Provisional Patent Application Serial No. 61 / 123,477, filed April 9, 2008. technical field [0005] The present invention relates generally to olefin metathesis, and more particularly, the present invention relates to imidazolines having trisubstituted or tetrasubstituted Tri- or tetra-substituted imidazolines as precursors of ring N-heterocyclic carbene (NHC) ligands Salts, containing gem-disubstituted imidazolines Organometallic ruthenium complexes of NHC ligands, containing tri- or tetra-substituted imidazolines Organometallic ruthenium complexes of NHC ligands, and olefin metathesi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D233/00C07D239/00
CPCC07F15/0046C07C67/333C07D233/06C08G61/08C07C67/475C07C2101/10C07C2601/10C07C69/74C07C69/007C07C69/157
Inventor 罗伯特·H·格拉布斯郑喆根让-巴普蒂斯特·布尔格凯文·库恩
Owner MATERIA
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