312599-02-3

Upstream product

• 67-56-1 methanol 
• 6828-41-7 3-hydroxy-4-phenylbutanoic acid 
• 103-82-2 phenylacetic acid 
• 37779-49-0 methyl 3-oxo-4-phenylbutanoate 
• 108-22-5 Isopropenyl acetate 
• 261348-04-3 3-oxo-4-phenyl-thiobutyric acid S-(2-acetylamino-ethyl) ester 
• 103-80-0 phenylacetyl chloride 
• 66696-84-2 5-(1-hydroxy-2-phenylethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione 

Downstream Products

• 1228099-82-8 (R)-2-(1'-benzyl-3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-3-yl)ethanol 
• 1228100-31-9 (R)-2-[1'-(3-phenylpropyl)-3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-3-yl]ethanol 
• 1228099-84-0 (R)-2-[1'-(cyclohexylmethyl)-3,4-dihydrospiro[[2]benzopyran-1,4'-piperidin]-3-yl]ethanol 
• 382135-54-8 (2R)-2-{(1S)-1-[formyl(tetrahydro-2H-pyran-2-yloxy)amino]-2-phenylethyl}-4-methylpentanoic acid 
• 382135-49-1 (3R,4S)-3-(2-methyl-1-propyl)-4-methylphenyl-1-(2-tetrahydro-2H-pyran-2-yloxy)azetidin-2-one 

Relevant academic research and scientific papers

CHIRAL ACETATE ENOLATE EQUIVALENT FOR THE SYNTHESIS OF β-HYDROXY ACIDS AND ESTERS: X-RAY CRYSTAL STRUCTURE OF RR,SS-5-C5H5)Fe(CO)(PPh3)(COCH2CH(OH)CH2CH3)>

The aluminium anolate derived from the iron acetyl complex 5-C5H5)Fe(CO)(PPh3)COCH3>, in contrast to the lithium enolate, undergoes highly strereoselective aldol reactions with aldehydes to generate RR,SS-β-hydroxyacyl complexes which on decomlexation liberate β-hydroxy acids or esters.Determination of the molecular structure of RR,SS-5-C5H5)Fe(CO)(PPh3)(COCH2CH(OH)CH2CH3> allowed assignment of the relative configuration of the new chiral centre.

On the basis of the phenethylamine skeleton chiral P, N, N ligand compound and its manufacturing method and application (by machine translation)

The present invention provides a chiral P based on the skeleton of the phenethylamine, N, N ligand compound and its manufacturing method and application, surfactant-ethylamine skeleton chiral P, N, N ligand compound of preparation method is as follows: under the protection of nitrogen, the chiral phenylethylamine - [...] compound with 2 - chloromethyl oxazole oxazoline compounds soluble in the reaction solvent, adding alkali, reflux reaction, filtering, desolvation, column chromatography to obtain the required chiral P, N, N ligand compound. In particular to the β - ketoacid ester compound in asymmetric catalytic hydrogenation reaction. The invention of the phenethylamine skeleton chiral P, N, β - keto ester N ligand can be applied to the asymmetric catalytic hydrogenation reaction, can be high yield and high enantio-selectively for the preparation of chiral β - hydroxy ester. (by machine translation)

Method for preparing chiral beta-hydroxy ester by Ir-catalyzed asymmetric hydrogenation

The invention provides a method for preparing a chiral beta-hydroxy ester compound by Ir-catalyzed asymmetric hydrogenation. The method for preparing the chiral beta-hydroxy ester compound comprises the steps as follows: in a glove box filled with nitrogen, [Ir(COD)Cl]2 and a chiral P, N, N ligand are dissolved in anhydrous methanol, stirring is performed at room temperature for 1 hour, and a Ir catalyst is generated; substrate beta-ketoester and a base additive are added, the mixture is placed in an autoclave and hydrogenated under certain reaction pressure; hydrogen gas is slowly released, separation with a silica gel column is performed after a solvent is removed, and product beta-hydroxy ester is obtained. The reaction for preparing chiral beta-hydroxy ester by Ir-catalyzed asymmetrichydrogenation of beta-ketoester has the advantages that conditions are mild, operation is easy, enantioselectivity of the product is high and the like.

Lipase-catalyzed kinetic resolution as key step in the synthesis of enantiomerically pure σ ligands with 2-benzopyran structure

In order to obtain enantiomerically pure σ1 receptor ligands with a 2-benzopyran scaffold an Oxa-Pictet-Spengler reaction with the enantiomerically pure 2-phenylethanol derivatives (R)-4 and (S)-4 was envisaged. The kinetic resolution of racemic alcohol (±)-4 using Amano Lipase PS-C II and isopropenyl acetate in tert-butyl methyl ether led to the (R)-configured alcohol (R)-4 in 42% yield with an enantiomeric excess of 99.6%. The (S)-configured alcohol (S)-4 was obtained by Amano Lipase PS-C II catalyzed hydrolysis of enantiomerically enriched acetate (S)-5 (76.9% ee) and provided (S)-4 in 26% yield and 99.7% ee. The absolute configuration of alcohol (R)-4 was determined by exciton coupled CD spectroscopy of the bis(bromobenzoate) (R)-7. The next important step for the synthesis of 2-benzopyrans 2 and 3 was the Oxa-Pictet-Spengler reaction of the enantiomerically pure alcohols (R)-4 and (S)-4 with piperidone ketal 8 and chloropropionaldehyde acetal 12. The conformationally restricted spirocyclic 2-benzopyrans 2 revealed higher σ1 affinity than the more flexible aminoethyl derivatives 3. The (R)- and (R,R)-configured enantiomers (R)-2 and (R,R)-3 represent the eutomers of this class of compounds with eudismic ratios of 4.8 (2b) and 4.5 (2c). High σ1/σ2 selectivity (>49) was found for the most potent σ1 ligands (R)-2b, (R)-2c, (R)-2d, and (S)-2d (Ki(σ1) 9–15?nM).

Asymmetric hydrogenation by RuCl2(R-Binap)(dmf)n encapsulated in silica-based nanoreactors

The Noyori catalyst RuCl2(R-Binap)(dmf)n has been successfully encapsulated in C-FDU-12 by using the active chlorosilane Ph2Cl2Si as the silylating agent. 31P-NMR results show that there is no strong interaction between the molecular catalyst and the solid support, thus the encapsulated molecular catalyst could move freely in the nanoreactor during the catalytic process. The solid catalyst exhibits high activity and enantioselectivity for the asymmetric hydrogenation of a series of β-keto esters due to the preserved intrinsic properties of RuCl2(R-Binap)(dmf)n encapsulated in the nanoreactor. The solid catalyst could be recycled by simple filtration and be reused at least four times.

Development of Chiral Spiro P-N-S Ligands for Iridium-Catalyzed Asymmetric Hydrogenation of β-Alkyl-β-Ketoesters

The chiral tridentate spiro P-N-S ligands (SpiroSAP) were developed, and their iridium complexes were prepared. Introduction of a 1,3-dithiane moiety into the ligand resulted in a highly efficient chiral iridium catalyst for asymmetric hydrogenation of β-alkyl-β-ketoesters, producing chiral β-alkyl-β-hydroxyesters with excellent enantioselectivities (95-99.9 % ee) and turnover numbers of up to 355 000. Bulkyness is the key: New chiral tridentate spiro P-N-S ligands (SpiroSAP) bearing a conformationally constrained 1,3-dithiane moiety were developed. Their iridium catalysts showed excellent enantioselectivities and activity (TON up to 355 000) for asymmetric hydrogenation of β-alkyl-β-ketoesters.

Highly efficient asymmetric transfer hydrogenation of ketones in emulsions

Ru-TsDPEN (TsDPEN = N-(p-tolylsulfonyl)-1,2-diphenylethylenediamine) catalyzed asymmetric transfer hydrogenation of ketones in emulsions is reported for the first time. The new protocol provides markedly enhanced activity and enantioselectivities (up to 99% ee) as compared with results when performed either in an aqueous medium or in common organic solvents.