Supercharge Your Innovation With Domain-Expert AI Agents!

Z-selective olefin metathesis catalysts and their synthetic procedure

一种复分解催化剂、烯烃的技术，应用在催化剂在Z-选择性烯烃复分解反应中的用途领域，能够解决限制用途、多合成步骤反应条件等问题

Active Publication Date: 2013-11-20
CALIFORNIA INST OF TECH
View PDF7 Cites 8 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Despite its excellent Z-type selectivity, its relatively high number of synthetic steps and generally demanding reaction conditions (for molybdenum and tungsten alkylidene catalysts) somewhat limit its usefulness in common organic syntheses

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Z-selective olefin metathesis catalysts and their synthetic procedure
  • Z-selective olefin metathesis catalysts and their synthetic procedure
  • Z-selective olefin metathesis catalysts and their synthetic procedure

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0135] Preparation of C-H-activated catalyst complexes from Ru-complex 4

[0136] By making (H 2 IMes)RuCl 2 [=CH-o-(O i Pr)C 6 h 4 ](4) and 2 equivalents of RCOOAg (R= t Bu, PhMe 2 C) reaction, obtain metal cyclization compound {[2-(CH 2 )-4,6-Me 2 (C 6 h 2 )](C 3 N 2 h 4 )-(Mes)}Ru(OCOR)[=CH-o-(O i Pr)C 6 h 4 ](R= t Bu(7a), PhMe 2 C(7b)) (Scheme 4), an air stable dark green solid. In this reaction, the disubstituted complex (8) was also observed at early reaction times. Subsequently, the C-H bond activates the methyl group of the mesityl group in the NHC ligand and forms the corresponding carboxylic acid, providing 7. The molecular structures of 7a and 7b were confirmed by X-ray crystallography. Such as Figure 4 with 5 Both 7a and 7b have 6-membered chelates formed from ruthenium and NHC ligands, as shown in .

[0137] Option 4

[0138]

[0139] The representative characterization data of complex 7a are as follows:

[0140] 1 HNMR (500MHz, C 6 D...

Embodiment 2

[0142] Preparation of C-H-activated catalyst complexes from Ru-complex 9

[0143] In the same manner as Scheme 4, (H 2 IMes)Ru(OTf) 2 [=CH-o-(O i Pr)C 6 h 4 ](9) (prepared as described in Krause, J.O.; Nuyken, O.; Wurst, K.; Buchmeiser, M.R. Chem. Eur. J. 2004, 10, 777) provides chelation in the reaction with the corresponding sodium salt Complexes {[2-(CH 2 )-4,6-Me 2 (C 6 h 2 )](C 3 N 2 h 4 )(Mes)}Ru(OCOR)[=CH-o-(O i Pr)C 6 h 4 ](R= t Bu(7a), Ph 2 MeC(7c), Ph 3 C(7d)) (Scheme 5). The products are all air-stable solids. In these reactions, the formation of the disubstituted complex (8) and subsequent formation of the carboxylic acid in the early stages of the reaction was also observed.

[0144] Option 5

[0145]

Embodiment 3

[0147] Preparation of C-H-activated catalyst complexes from Ru-complex 10

[0148] By making the (H 2 IMesDipp)RuCl 2 [=CH-o-(O i Pr)C 6 h 4 ](10) reacted with silver pivalate to obtain {[2-(CH 2 )-4,6-Me 2 (C 6 h 2 )](C 3 N 2 h 4 )(Dipp)}Ru(OCO t Bu)[=CH-o-(O i Pr)C 6 h 4 ](11) (Scheme 6), an air-stable dark green solid. During this reaction, disubstituted complex (12) was formed without any observed complex originating from activation of the C—H bond in the 2,6-diisopropylphenyl group. The crystal structure of 11 determined by X-ray crystallography ( Image 6 ) shows a 6-membered chelate and clearly shows that the methyl group of the mimidyl group in the NHC ligand has undergone C-H bond activation.

[0149] Option 6

[0150]

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to C-H activated olefin metathesis catalyst compounds, the preparation of such compounds, and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, the use of such catalysts in Z selective olefin metathesis reactions. In general, the catalyst compounds of the invention comprise a Group 8 metal (M), an alkylidene moiety (=CR1R2), or more generally (=(C)mC R1R2), an anionic ligand (X1), two or three neutral ligands (L1, L2, and L3) and a 2-electron anionic donor bridging moiety (Q*) that forms a chelate ring structure in conjunction with L1 and M. Such catalysts generally correspond to the formula X1(L3)kL2L1Q*M=(C)mCR1R2, wherein X1 is any anionic ligand, L1, L2, and L3 are, independently, any neural electron donor ligand, k is 0 or 1, m is 0, 1, or 2, Q* is a 2-electron anionic donor bridging moiety linking L1 and M, M is a Group 8 transition metal, and R1 and R2 are, independently, hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom- containing hydrocarbyl, or functional groups. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

Description

[0001] related application [0002] This application claims U.S. Provisional Application Serial No. 61 / 432,849 (CIT-5776-P), filed January 4, 2011, U.S. Provisional Application Serial No. 61 / 433,949 (CIT-5776-P), filed January 18, 2011 P2) and the priority benefit of US Provisional Application Serial No. 61 / 515,262 (CIT-5776-P3), filed August 4, 2011, each of which is incorporated herein by reference. technical field [0003] The present invention relates generally to C-H activated olefin metathesis catalyst compounds, to the preparation of such compounds, and to the use of such catalysts in the metathesis of olefins and olefinic compounds, and more particularly to the use of such catalysts in Z-selective olefin metathesis Use in metathesis reactions. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemical chemistry. [0004] Statement of Federal Government Funding [0005] The US Government has certain ri...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/46C07F15/00C07C6/02
CPCB01J31/2278B01J2231/543C07F15/0046B01J2531/0261B01J31/2208B01J31/2273B01J31/2226C07C6/04C07C2531/22C07C67/343B01J31/223B01J2531/821C07C15/50C07C69/157C07C69/593B01J31/22B01J31/12C07C6/02B01J31/2295Y02P20/52
Inventor 远藤浩司本杰明·基思·凯茨迈尔斯·本顿·赫伯特佩尔斯玛·拉西科拉尔·帕特尔罗伯特·霍华德·格拉布斯
Owner CALIFORNIA INST OF TECH
Features
  • R&D
  • Intellectual Property
  • Life Sciences
  • Materials
  • Tech Scout
Why Patsnap Eureka
  • Unparalleled Data Quality
  • Higher Quality Content
  • 60% Fewer Hallucinations
Social media
Patsnap Eureka Blog
Learn More

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2025 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com