Materia, Inc.

Elevance Renewable Sciences, Inc.

Other

California Institute of Technology

Wilmar Trading Pte Ltd.

Schrodi, Yann

Pederson, Richard L.

Tupy, Michael J.

Kaido, Hiroki

Yann Schrodi

Richard L Pederson

Michael John Tupy

Hiroki Kaido

Christopher M Haar

Jason K Woertink

David E Gindelberger

Robert H Grubbs

Timothy Walter Abraham

Choon Woo Lee

Mark S Trimmer

Jacob Berlin

Daniel P Sanders

Andrew Hejl

Ian C Stewart

Thay Ung

James C Anderson

William H Sperber

Jill Louise Zullo

Alexandre A Pletnev

Earl H Wagener

Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

Methods of making organic compounds by metathesis

Chelating ligand precursors for the preparation of olefin methathesis catalysts are disclosed. The resulting catalysts are air stable monomeric species capable of promoting various methathesis reactions efficiently, which can be recovered from the reaction mixture and reused. Internal olefin compounds, specifically beta-substituted styrenes, are used as ligand precursors. Compared to terminal olefin compounds such as unsubstituted styrenes, the beta-substituted styrenes are easier and less costly to prepare, and more stable since they are less prone to spontaneous polymerization. Methods of preparing chelating-carbene methathesis catalysts without the use of CuCl are disclosed. This eliminates the need for CuCl by replacing it with organic acids, mineral acids, mild oxidants or even water, resulting in high yields of Hoveyda-type methathesis catalysts. The invention provides an efficient method for preparing chelating-carbene metathesis catalysts by reacting a suitable ruthenium complex in high concentrations of the ligand precursors followed by crystallization from an organic solvent.

Chelating carbene ligand precursors and their use in the synthesis of metathesis catalysts

Synthetic methods for the in-situ formation of olefin metathesis catalysts are disclosed, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. In one aspect, a method is provided for synthesizing an organometallic compound of the formula comprising contacting a precursor compound of the formula (XXMLLL)with an acetylenic compound comprising a chelating moiety, optionally, in the presence of a neutral electron donor, wherein M is a Group 8 transition metal, L, L, L, and Lare neutral electron donors, Xand Xare anionic ligands, j is 1, 2, or 3; k is zero, 1, or 2; m is zero or 1; n is 1 or 2; and i is an integer; with the proviso that k is zero when the precursor compound is contacted with the acetylenic compound in the presence of the neutral electron donor, and Rand Rare independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein Rand Rare linked and together form one or more cyclic groups, Rand Lare linked and together form one or more cyclic groups, and any other two or more of X, X, L, L, L, R, and Rcan be taken together to form one or more cyclic groups. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

Method for in-situ formation of metathesis catalysts

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

The invention provides novel organometallic complexes useful as olefin metathesis catalysts. The complexes have an N-heterocyclic carbene ligand and a chelating carbene ligand associated with a Group 8 transition metal center. The molecular structure of the complexes can be altered so as to provide a substantial latency period. The complexes are particularly useful in catalyzing ring closing metathesis of acyclic olefins and ring opening metathesis polymerization of cyclic olefins.

Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand

The invention is directed to methods of making organic compounds by metathesis and hydrocyanation. The method of the invention may be used, for example, to make industrial important organic compounds such as diacids, diesters, acid-amines, acid-alcohols, acid-nitriles, ester-amines, ester-alcohols, and ester-nitriles.

Methods of making organic compounds by metathesis and hydrocyanation

Disclosed are improved methods for conducting metathesis utilizing polyunsaturated fatty acid compositions (e.g., polyunsaturated fatty acid polyol esters, polyunsaturated fatty acids, polyunsaturated fatty esters, and mixtures), such as those found in naturally occurring oils and fats, as the starting material. The inventive methods involve hydrogenation of polyunsaturated fatty acid compositions prior to metathesis, thereby providing partially-hydrogenation compositions having a relatively higher amount of monounsaturated fatty acid species. The partially hydrogenated composition can then be subjected to metathesis to provide a metathesis product composition containing industrially useful compounds.

Metathesis methods involving hydrogenation and compositions relating to same

This disclosure relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by an olefin metathesis catalyst. According to one aspect, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting, in the presence of a ruthenium alkylidene metathesis catalyst, an olefinic substrate comprised of at least one internal olefin with a cross metathesis partner comprised of an alpha olefinic reactant, under reaction conditions effective to allow cross-metathesis to occur, wherein the reaction conditions include a reaction temperature of at least 35&#xb0; C. The methods, compositions, reactions and reaction systems herein disclosed have utility in the fields of catalysis, organic synthesis, and industrial chemistry.

Synthesis of terminal alkenes from internal alkenes via olefin metathesis

The invention relates to ruthenium alkylidene complexes having an N-heterocyclic carbene ligand comprising a 5-membered heterocyclic ring having a carbenic carbon atom and at least one nitrogen atom contained within the 5-membered heterocyclic ring, wherein the nitrogen atom is directly attached to the carbenic carbon atom and is substituted by a phenyl ring, and wherein the phenyl ring has a hydrogen at either or both ortho positions and is substituted at at least one ortho or meta position. The invention also relates to an olefin metathesis reactions and particularly to the preparation of tetra-substituted cyclic olefins via a ring-closing metathesis.

Organometallic ruthenium complexes and related methods for the preparation of tetra-substituted and other hindered olefins

Growing community of inventors

Agoura Hills, CA, United States of America

Yann Schrodi