Novomer, Inc.

Massachusetts Institute of Technology

Saudi Aramco Technologies Company

Gabriel E Job

Jay J Farmer

Scott D Allen

Stephen L Buchwald

Artis Klapars

Jon Clarence Antilla

Fuk Y Kwong

Gero Nordmann

Edward J Hennessy

Anna E Cherian

Martina Wolter

Christopher A Simoneau

Ronald Valente

Martina Uhlenbrock

Edward Hennessy

The present invention describes metal salen complexes having dianionic counterions. Such complexes can be readily precipitated and provide an economical method for the purification and isolation of the complexes, and are useful to prepare novel polymer compositions.

Salen complexes with dianionic counterions

Among other things, the present invention encompasses methods of synthesizing salicylaldehyde derivatives comprising the steps of: a) providing salicylaldehyde or a derivative thereof, b) forming an anhydro dimer of the provided salicylaldehyde compound, c) performing one or more chemical transformations on the anhydro dimer and d) hydrolyzing the anhydro dimer to provide a salicylaldehyde derivative different from that provided in step (a).

Synthesis of substituted salicylaldehyde derivatives

The present invention provides novel metal complexes, methods of making, and methods of using the same.

Metal complexes

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

Catalysts and methods for polymer synthesis

The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods, such as the reaction of Z-X with C(L)(R)(R')in the present of a catalyst and a base, thereby forming C(Z)(R)(R&#x2032;); wherein X represents I, Cl, alkylsulfonate, or arylsulfonate; Z represents optionally substituted aryl, heteroaryl or alkenyl; L represents H or a negative charge; catalyst comprises a copper atom or ion, and a ligand, wherein the ligand is an optionally substituted aryl alcohol, alkyl amine, 1,2-diamine, 1,2-aminoalcohol, 1,2-diol, imidazolium carbene, pyridine, or 1,10-phenanthroline; the ligand is a chelating ligand; and the base represents a Bronsted base; R represents H, optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; R&#x2032; represents independently for each occurrence H, alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl, formyl, acyl, &#x2014;COR&#x2033;, &#x2014;C(O)N(R), sulfonyl, &#x2014;P(O)(OR&#x2033;), &#x2014;CN, or &#x2014;NO; R&#x2033; represents independently for each occurrence optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; and C(R&#x2032;)(R) taken together may represent nitrile.

Copper-catalyzed formation of carbon-heteroatom and carbon&#x2014;carbon bonds

The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds

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Ithaca, NY, United States of America

Gabriel E Job