771476-32-5

Upstream product

• 66-25-1 hexanal 
• 586-96-9 Nitrosobenzene 
• 104-53-0 3-phenyl-propionaldehyde 
• 722-04-3 N-(3-dimethylaminopropyl)-N’-phenylthiourea 
• 103-72-0 phenyl isothiocyanate 

Downstream Products

• 608130-29-6 (R)-2-(N-phenyl-aminooxy)-hexan-1-ol 
• 867061-73-2 (6R)-6-butyl-2-phenyl-3,6-dihydro-2H-[1,2]oxazine 
• 110013-17-7 5R-butyl-2(5H)-furanone 
• 107797-19-3 (R)-(E)-ethyl 4-hydroxyoct-2-enoate 

Relevant academic research and scientific papers

SYNTHETIC METHOD OF EPOGYMNOLACTAM AND INTERMEDIATE THEREOF

PROBLEM TO BE SOLVED: To provide a synthetic method of an epogymnolactam and an α,β-unsaturated-γ-lactone derivative, which is simple to operate and is more efficient than the conventional synthetic method. SOLUTION: The synthetic method comprises: subjec

Organocatalytic Asymmetric Tandem α-Aminooxylation–Henry Reactions for the Synthesis of 1,2-Diols: Total Synthesis of (–)-l-threo-Sphinganine

A new and rapid asymmetric synthesis of anti- and syn-β,γ-dihydroxynitroalkanes through an organocatalytic tandem α-aminooxylation–Henry reaction is described. The target diol derivatives were synthesized in good yields, with excellent enantioselectivitie

Organocatalytic sequential α-aminoxylation and cis-Wittig olefination of aldehydes: Synthesis of enantiopure γ-butenolides

A short route to enantiopure γ-butenolides (up to 99% ee) has been developed from readily available starting materials. The strategy involves a sequential organocatalytic α-aminoxylation followed by cis-Wittig olefination of aldehydes. The utility of this protocol has been demonstrated in the asymmetric synthesis of trans-(+)-cognac lactone with high enantiomeric purity.

Continuous proline catalysis via leaching of solid proline

Herein, we demonstrate that a homogeneous catalyst can be prepared continuously via reaction with a packed-bed of a catalyst precursor. Specifically, we perform continuous proline catalyzed α-aminoxylations using a packed-bed of L-proline. The system relies on a multistep sequence in which an aldehyde and thiourea additive are passed through a column of solid proline, presumably forming a soluble oxazolidinone intermediate. This transports a catalytic amount of proline from the packed-bed into the reactor coil for subsequent combination with a solution of nitrosobenzene, affording the desired optically active α-aminooxy alcohol after reduction. To our knowledge, this is the first example in which a homogeneous catalyst is produced continuously using a packedbed. We predict that the method will not only be useful for other L-proline catalyzed reactions, but we also foresee that it could be used to produce other catalytic species in flow.

Imidazolium ion-tagged proline organocatalyst for α-aminoxylation of aldehydes and ketones in ionic liquids

A novel imidazolium ion-tagged L-proline catalyst has been developed. The asymmetric α-aminoxylation of aldehydes and ketones with excellent enantioselectivities, up to 99% ee, and high yields in ionic liquids has been achieved. The system can be easily recycled and reused for at least six times without significant loss of yields and enantioselectivity.

Enantioselective synthesis of syn / anti -1,3-amino alcohols via proline-catalyzed sequential α-aminoxylation/α-amination and horner-wadsworth-emmons olefination of aldehydes

(Figure presented) A novel and general method for asymmetric synthesis of both syn/anti-1,3-amino alcohols is described. The method uses proline-catalyzed sequential α-aminoxylation/ α-amination and Horner-Wadsworth-Emmons (HWE) olefination of aldehydes as the key step. By using this method, a short synthesis of a bioactive molecule, (R)-1-((S)-1-methylpyrrolidin-2-yl)-5- phenylpentan-2-ol, is also accomplished.

Highly enantioselective l-thiaproline catalyzed α-aminoxylation of aldehydes in aqueous media

Highly enantioselective L-thiaproline catalyzed α-aminoxylation of aldehydes in the presence of water and tetrabutylammonium bromide followed by in situ reduction to afford the respective α-aminoxy alcohols has been developed in good to high yields (74-88%) and excellent enantioselectivities (93->99%).

ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS

The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo--selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R", NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ("hydrocarbyl") group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R" are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R" form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R" are attached; and wherein said compound is free from a metal catalyst.

A highly selective, organocatalytic route to chiral dihydro-1,2-oxazines

(Chemical Equation Presented) The organocatalyzed asymmetric synthesis of chiral dihydro-1,2-oxazines from achiral starting materials proceeds in moderate to excellent yields and excellent enantioselectivity. This sequential reaction gives the desired pro

The direct catalytic asymmetric α-aminooxylation reaction: Development of stereoselective routes to 1,2-diols and 1,2-amino alcohols and density functional calculations

Proline-catalyzed direct asymmetric α-aminooxylation of ketones and aldehydes is described. The proline-catalyzed reactions between unmodified ketones or aldehydes and nitrosobenzene proceeded with excellent diastereo- and enantioselectivities. In all cases tested, the corresponding products were isolated with > 95% ees. Methyl alkyl ketones were regiospecifically oxidized at the methylene carbon atom to afford enantiomerically pure α-aminooxylated ketones. In addition, cyclic ketones could be α,α′-dioxidized with remarkably high selectivity, furnishing the corresponding diaminooxylated ketones with > 99% ees. The reaction mechanism of the proline-catalyzed direct asymmetric α-aminooxylation was investigated, and we performed density functional theory (DFT) calculations in order to investigate the nature of the plausible transition states further. We also screened other organocatalysts for the asymmetric α-oxidation reaction and found that several proline derivatives were also able to catalyze the transformation with excellent enantioselectivities. Moreover, stereoselective routes for the synthesis of monoprotected vicinal diols and hydroxyketones were found. In addition, short routes for the direct preparation of enantiomerically pure epoxides and 1,2-amino alcohols are presented. The direct catalytic α-oxidation is also a novel route for the stereoselective preparation of β-adrenoreceptor antagonists.