63857-19-2

Upstream product

• 103-25-3 3-phenylpropanoic acid methyl ester 
• 109-94-4 formic acid ethyl ester 
• 103-26-4 Methyl cinnamate 
• 201230-82-2 carbon monoxide 
• 591-50-4 iodobenzene 
• 15484-46-5 methyl 2-hydroxymethylacrylate 
• 107-31-3 Methyl formate 
• 103-26-4 methyl cinnamate 

Downstream Products

• 63857-13-6 2-(Diisopropyl-hydrazonomethyl)-3-phenyl-propionic acid methyl ester 
• 1233560-08-1 6-(4-benzyl-5-oxo-2,5-dihydro-1H-pyrazol-1-yl)-N-ethyl-N-phenylpyridine-3-sulfonamide 
• 709673-94-9 (R)-2-benzyl-3-hydroxypropanoic acid methyl ester 
• 63857-12-5 2-(Diethyl-hydrazonomethyl)-3-phenyl-propionic acid methyl ester 

Relevant academic research and scientific papers

Insertion of Alkylidene Carbenes into B-H Bonds

We have developed a protocol for insertion of alkylidene carbenes into the B-H bonds of amine-borane adducts, enabling, for the first time, the construction of C(sp2)-B bonds by means of carbene-insertion reactions. Various acyclic and cyclic alkenyl borane-amine adducts were prepared from readily accessible starting materials in good to high yields and were subsequently subjected to a diverse array of functional group transformations. The unprecedented spiro B-N heterocycles prepared in this study have potential utility as building blocks for the synthesis of pharmaceuticals. Preliminary mechanistic studies suggest that insertion of the alkylidene carbenes into the B-H bonds of the amine-borane adducts proceeds via a concerted process involving a three-membered-ring transition state.

DERIVATIVES OF 2-PYRIDIN-2-YL-PYRAZOL-3(2H)-ONE, PREPARATION AND THERAPEUTIC USE THEREOF AS HIF ACTIVATORS

The present invention relates to novel substituted dihydropyrazolone derivatives, to their preparation and to their therapeutic use as activators of the transcription factor HIF.

Highly regioselective rhodium-catalysed hydroformylation of unsaturated Esters: The first practical method for quaternary selective carbonylation

Highly regioselective hydroformylation of unsaturated esters can be achieved when a highly reactive, ligand-modified, rhodium catalyst is employed near ambient temperatures (15-50°C) and pressures over 30 bar. The use of 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane shows distinct advantages over other commonly applied phosphanes in terms of reaction rate, and regio- and chemoselectivity. Hydroformylation of a range 1,1-di- and 1,1,2-trisubstituted unsaturated esters yields quaternary aldehydes that are forbidden products according to Keulemans Rule. The aldehydes can be reductively aminated with molecular hydrogen to give β-amino acid esters in high yield. The overall green chemical process involves converting terminal alkynes into unusual β-amino acid esters with only water generated as an essential byproduct. This catalytic system has also been applied to the hydroformylation of simple 1,2-disubstitued unsaturated esters, which have been hydroformylated with excellent α-selectivity and good chemo-selectivity for the first time.

The Heck reaction in the presence of molecular oxygen

Palladium-catalyzed reaction of CH2=C(R)COOMe (R=H or CH2OH) with PhI in the presence of NEt3 under O2 induces the oxidative dealkylation of NEt3, affording either methyl 3-diethylaminopropionate (3) or methyl (Z)-2-benzyl-3-(N,N′-diethylamino)propenate (6), in case of R=H or R=CH2OH, respectively.

Catalytic TMSCl promoted powerful aldol addition and Claisen condensation mediated by TiCl4/Bu3N agent: Comparison and evaluation with the Mukaiyama aldol addition

TMSCl catalyst (0.05 equiv) significantly promoted the TiCl4/Bu3N-mediated direct cross aldol additions of sterically crowded ketones and α-hetero substituted ketones, and also the direct Claisen condensation between methyl esters.

TiCl4/Bu3N/(catalytic TMSOTf): Efficient agent for direct aldol addition and claisen condensation

TiCl4/Bu3N conducts highly efficient cross aldol additions between different ketones and between ketones and aldehydes, in good to excellent yields with high syn-stereoselectivities. As an extension, direct Claisen condensation between methyl esters was also promoted by TiCl4/Bu3N with 0.05 equiv of TMSOTf co-catalyst.

Hydroformylation of cinnamic acid derivatives catalyzed by rhodium complexes

The hydroformylation of methyl cinnamate catalyzed by various rhodium complexes affords the aldehyde 1a with good chemo- and regio-selectivity, while in the case of methyl p-chlorocinnamate the predominant reaction is the substrate hydrogenation. Higher yields of the desired aldehydes 1a and 1b are obtained by hydroformylation of the cinnamaldehyde and p-chlorocinnamaldehyde diethylacetal, respectively, under the same reaction conditions. These aldehyde products are valuable drug precursors.

THE SELECTIVE CLAISEN AND DIECKMANN ESTER CONDENSATION PROMOTED BY DICHLOROBIS(TRIFLUOROMETHANESULFONATO)TITANIUM(IV)

Inter and intramolecular condensations (the Claisen and the Dieckmann condensations) between ester functions have been performed by the combined use of dichlorobis(trifluoromethanesulfonato)titanium(IV) (=dichlorobis(triflato)titanium(IV)) and tertiary amine under mild reaction conditions.These results led to the development of the selective (crossed) Claisen and Dieckmann ester condensation between methoxymethyl ester and methyl ester, in that, dichlorobis(triflato)titanum(IV) contribute to control the direction of the reaction.

DICHLORO-BIS(TRIFLUOROMETHANESULFONATO)TITANIUM(IV) AS AN EFFECTIVE PROMOTER IN THE CLAISEN ESTER CONDENSATION

Inter- and intra-molecular condensation (the Claisen and the Dieckmann condensations) between ester functions have been effected by the combined use of dichloro-bis(trifluoromethanesulfonato)titanium(IV) and tertiary amine under mild conditions.

HYDROFORMYLATION OF OLEFINS WITH PARAFORMALDEHYDE CATALYZED BY RHODIUM COMPLEXES

The addition of formaldehyde to olefins is efficiently catalyzed by RhH2(O2COH)2 and gives the corresponding aldehydes in neutral solution.