Abstract: This disclosure concerns the metabolic engineering of microorganisms to provide biosynthetic methods for the production of insect pheromones and precursors thereof in a scalable and eco-friendly fermentation reaction; for example, by converting saturated or unsaturated substrate feedstocks utilizing exogenous metabolic machinery.

Abstract: Methods for preparing conjugated dienes are described. An ?,?-unsaturated E olefin intermediate may be prepared via cross-metathesis using a catalyst comprising a transition metal (e.g., ruthenium), a first carbene ligand (e.g., a substituted indenylidene) and an N-heterocyclic carbene ligand (e.g., an imidazolidinylidene). The catalyst further includes a phenylphosphine ligand, a tri(isopropoxy)phosphine ligand, a dimethylsulfoxide ligand, an acetonitrile ligand, or a pyridine ligand. Following the cross metathesis-step, the ?,?-unsaturated aldehyde intermediate may be converted to the conjugated diene product via reaction with a phosphonium ylide. Products obtained via the methods of the disclosure include (7E,9Z)-dodeca-7,9-dien-1-yl acetate, a pheromone produced by Lobesia botrana (European grapevine moth), and other insect pheromones.

Abstract: Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.

Abstract: Methods for the preparation of alkenes including insect pheromones are described. The methods include homologation reactions employing reagents such as 1,3-diesters, epoxides, cyanoacetates, and cyanide salts for elongation of starting materials and intermediates by one or two carbon atoms. The alkenes include insect pheromones useful in a number of agricultural applications.

Abstract: Methods for preparation of olefins, including 8- and 11-unsaturated monoenes and polyenes, via transition metathesis-based synthetic routes are described. Metathesis reactions in the methods are catalyzed by transition metal catalysts including tungsten-, molybdenum-, and ruthenium-based catalysts. The olefins include insect pheromones useful in a number of agricultural applications.

Abstract: The present invention provides methods by which trans-(1R,2S)-2-(3,4-difluorophenyl)-cyclopropylamine and related cyclopropane compounds are prepared using synthetic strategies that include a biocatalytic cyclopropanation step.

Abstract: Fluoroalkyl-substituted, nitrogen-containing, aryl heterocyclic compounds are provided. The compounds are derivatives of pyridine, pyrimidine, or pyrazine, and have two or three functional groups bonded to the heterocyclic ring, including a perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, or difluoromethyl group. Methods of making the compounds using a copper reagent are also provided.

Abstract: Compounds having therapeutic potential as androgen receptor modulators, and methods of making such compounds, are provided. The compounds are structurally related to bicalutamide but bear at least one difluoromethyl or C2 to C5 perfluoroalkyl group instead of a trifluoromethyl group.

Abstract: Methods for chemically transforming compounds using a mutated enzyme are provided, and more particularly a method for the production of an amine from a target ketone. The methods comprise creating a mutated enzyme that catalyzes the reductive amination of the target ketone under conditions sufficient to permit the formation of the desired amine to thereby produce the amine.

Abstract: Polypeptides capable of catalyzing the reductive amination of a 2-ketoacid to its corresponding D-amino acid are provided. The polypeptides can be prepared by mutagenesis of, e.g., a diaminopimelate dehydrogenase. Also provided is a method of making a D-amino acid using a catalytically active polypeptide, wherein a 2-ketoacid is allowed to contact the polypeptide in the presence of a nicotinamide cofactor and ammonia or an ammonia source.

Abstract: Polypeptides capable of catalyzing the reductive amination of a 2-ketoacid to its corresponding D-amino acid are provided. The polypeptides can be prepared by mutagenesis of, e.g., a diaminopimelate dehydrogenase. Also provided is a method of making a D-amino acid using a catalytically active polypeptide, wherein a 2-ketoacid is allowed to contact the polypeptide in the presence of a nicotinamide cofactor and ammonia or an ammonia source.

Abstract: A method for producing a hydroxy-amino ester, or derivative thereof, is provided. A substituted ?-ketodiester having a ketone group and two ester functional groups is contacted with a ketoreductase under conditions permitting the reduction of the ketone group to an alcohol. Only one of the ester functional groups is regioselectively hydrolyzed to the corresponding carboxylic acid, whereby a non-hydrolyzed ester functional group remains. The carboxylic acid is converted to an amine or a derivative thereof to produce a hydroxy-amino ester or derivative thereof. A number of novel hydroxy-amino esters are prepared by the method.

Abstract: Methods for chemically transforming compounds using a mutated enzyme are provided, and more particularly a method for the production of an amino acid from a target 2-ketoacid, the production of an amine from a target ketone and the production of an alcohol from a target ketone. The methods comprise creating a mutated enzyme that catalyzes the reductive amination or transamination of the target 2-ketoacid or ketone or the reduction of the ketone and providing the mutated enzyme in a reaction mixture comprising the target 2-ketoacid or ketone under conditions sufficient to permit the formation of the desired amino acid, amine or alcohol to thereby produce the amino acid, amine or alcohol.

Abstract: Pro-dyes of direct dyes having an enzymatically-labile functionality, e.g. glutaramide derivatives of direct dyes of formula (I) or their physiologically acceptable salts, are described, as well as compositions for dyeing keratinous fibers containing these pro-dyes, as well as compositions for dyeing keratinous fibers containing a combination of at least one pro-dye and at least one enzyme capable of cleaving the glutaramide functionality in the pro-dye. A method for dyeing keratinous fibers with the aforementioned dyeing compositions is also described.

Abstract: Hydroxy-amino acids are provided and are prepared by contacting a substituted ?-ketodiester having a ketone group and two ester functional groups with a ketoreductase under conditions permitting the reduction of the keytone group to an alcohol. Only one of the ester functional groups is regioselectively hydrolyzed to the corresponding carboxylic acid, whereby a non-hydrolyzed ester functional group remains. The carboxylic acid is converted to an amine to produce a hydroxy-amino acid.

Abstract: A method for providing a time-dependent decrease of pH in a cosmetic composition is described. A method of permanently shaping hair is also described, in which, immediately prior to use, an enzyme that catalyzes an acid-generating reaction with a non-ester substrate is added to an alkaline composition, which contains the non-ester substrate, to form a ready-to-apply cosmetic composition. Then the hair, before and/or after it is put in a desired shape, is treated with the ready-to-apply cosmetic composition and, after a period of action, is rinsed from the hair with water. Thereafter the hair is oxidatively treated, rinsed again with water, optionally put in a water wave and dried. Preferably the enzyme and the non-ester substrate are selected so that the initial pH decreases by at least 0.5 pH units within a time interval of from 5 to 40 minutes.

Abstract: The agent for dyeing keratin fibers contains one or more aryl and/or benzyl alcohols, one or more oxidizing enzymes, especially vanillyl oxidase, derivatives of vanillyl oxidase or galactose oxidase, and a nucleophilic compound that forms a dye for dyeing keratin fibers in the presence of the alcohols and enzymes. A method for dyeing keratin fibers with this agent is also disclosed. Two-component kits for performing the method of dyeing keratin fibers include a first compenent (A) and a second component (B) separate from the first component. The first component (A) includes the nucleophilic compound, the alcohol and optionally the oxidizing enzyme. The second component (B) includes the oxidizing enzyme when it is not included in the first component or more alcohol.

Abstract: A methods for producing a hydroxy-amino acid or derivative thereof, such as statine, phenylstatine or isostatine, is provided. A substituted &bgr;-ketodiester having a ketone group and two ester functional groups is contacted with a ketoreductase under conditions permitting the reduction of the ketone group to an alcohol. Only one of the ester functional groups is regioselectively hydrolyzed to the corresponding carboxylic acid, whereby a non-hydrolyzed ester functional group remains. Either the carboxylic acid or the non-hydrolyzed ester functional group is converted to an amine or a derivative thereof to produce a hydroxy-amino acid or derivative thereof.

Abstract: Methods for producing single diastereomers of isoleucine in high stereochemical purity are provided. D-isoleucine is produced by converting (R)-2-methylbutyraldehyde to a diastereomeric mixture of D-isoleucine hydantoin and L-allo-isoleucine hydantoin (5S-[(R)-1-methylpropyl]hydantoin) under conditions whereby no significant racemization of the chiral center in (R)-2-methylbutyraldehyde occurs, followed by contacting said diastereomeric hydantoin mixture with a D-hydantoinase to stereoselectively hydrolyze any D-isoleucine hydantoin in the mixture to the corresponding N-carbamoyl-D-isoleucine, preferably under conditions permitting the simultaneous epimerization of the chiral center at C-5 of the hydantoin. The simultaneous epimerization permits the reaction to be carried out to substantial completion so that the diastereomeric hydantoin mixture is converted to N-carbamoyl-D-isoleucine in high yield. The N-carbamoyl-D-isoleucine is then decarbamoylated to produce D-isoleucine.

Abstract: A method for producing D-allo-isoleucine is provided. The method comprises converting L-isoleucine to the corresponding hydantoin. A mixture containing the hydantoin is contacted with a D-hydantoinase to stereoselectively hydrolyze any D-allo-isoleucine hydantoin in the mixture to the corresponding N-carbamoyl-D-allo-isoleucine. The N-carbamoyl-D-allo-isoleucine is decarbamoylated to produce D-allo-isoleucine. Preferably the contacting of the hydantoin with a D-hydantoinase is carried out under conditions permitting the simultaneous epimerization of the chiral center at C-5 of the hydantoin.