120672-87-9

Upstream product

• 5680-79-5 glycine ethyl ester hydrochloride 
• 1122-91-4 4-bromo-benzaldehyde 

Downstream Products

• 139574-95-1 2-{[1-(4-Bromo-phenyl)-meth-(E)-ylidene]-amino}-4-(methoxy-methyl-phosphinoyl)-butyric acid methyl ester 
• 138037-93-1 (2R,4R,5S)-dimethyl 5-(4-bromophenyl)pyrrolidine-2,4-dicarboxylate 
• 138037-93-1 (2S,4S,5R)-5-(4-Bromo-phenyl)-pyrrolidine-2,4-dicarboxylic acid dimethyl ester 
• 1166397-79-0 trimethyl (2R,3S,4R,5S)-5-(4-bromophenyl)pyrrolidine-2,3,4-tricarboxylate 
• 1241941-49-0 methyl 5-(4-bromophenyl)-4-(2,2,2-trifluoroacetyl)-1H-pyrrole-2-carboxylate 
• 1221295-51-7 C₂₀H₂₀BrNO₃ 
• 1100793-05-2 methyl (1S,3R,3aS,6aR)-3-(4-bromophenyl)-octahydro-4-oxocyclopenta[c]pyrrole-1-carboxylate 
• 1279107-34-4 (4R,6S,7R)-7-ethyl 4-methyl 6-(4-bromophenyl)-5-azaspiro[2.4]heptane-4,7-dicarboxylate 
• 1250954-14-3 (2'R,3S,4'R,5'R)-methyl 2'-(4-bromophenyl)-2-oxo-4'-phenylspiro[indoline-3,3'-pyrrolidine]-5'-carboxylate 
• 1309923-04-3 (2R,5R)-4,4-diethyl 2-methyl 5-(4-bromophenyl)-3-(2,2-diphenylvinylidene)-pyrrolidine-2,4,4-tricarboxylate 
• 1319726-80-1 (1R,3R,4R,5R)-methyl 1-(4-bromophenyl)-6-oxo-4-phenyl-2-azaspiro[4.4]nonane-3-carboxylate 
• 1319726-91-4 (1R,3R,4R,5R)-methyl 1,4-bis(4-bromophenyl)-6-oxo-2-azaspiro[4.4]nonane-3-carboxylate 
• 1340585-67-2 (2R,3R,4R,5S)-4-tert-butyl 2-methyl 5-(4-bromophenyl)-3-(trifluoromethyl)pyrrolidine-2,4-dicarboxylate 
• 1352713-22-4 (2R,3R,4S,5R)-dimethyl 5-(4-bromophenyl)-3-(phenylsulfonyl)pyrrolidine-2,4-dicarboxylate 

Relevant academic research and scientific papers

Diversity oriented synthesis of pyrrolidines via natural carbohydrate solid acid catalyst

Natural carbohydrate scaffold catalyzed diastereoselective synthesis of functionalized pyrrolidines have been developed via 1,3-dipolar cycloaddition of azomethine ylides derived from α-imino esters with dienes or dipolarophiles. Naturally most abundant carbohydrates, like cellulose and starch, were converted into their sulfuric acid derivative, which are exhibiting efficient catalytic properties, along with excellent cost effectivity and recyclability. The advantages of this methodology are diversity oriented metal free synthesis of functionalized pyrrolidines, mild reaction condition, high diasteroselectivity and yield.

Silicon-based Bulky Group?Tuned Parallel Kinetic Resolution in Copper-Catalyzed 1,3-Dipolar Additions

The development of new strategies or reaction processes that tease new reactivity of functional groups continues to spur synthetic chemists toward innovative solutions that access new compounds. Herein, we find that the silicon-based bulky group enables a 1,3-dipolar addition?initiated parallel kinetic resolution (PKR) to occur unexpectedly, leading to the highly enantioselective synthesis of two structurally different types of amino acid derivatives via chemodivergent [3+2] cycloaddition reactions and tandem conjugate addition-elimination reaction respectively. The resulting and structurally divergent enantioenriched amino acid derivatives that contain four contiguous stereogenic centers and an all-carbon quaternary center were obtained with up to 99% ee with >95:1 dr and good yields. (Figure presented.).

Synthesis of Azacyclic Nucleoside Analogues via Asymmetric [3 + 2] Cycloaddition of 9-(2-Tosylvinyl)-9H -purines

With 9-(2-tosylvinyl)-9H-purines as the dipolarophiles, a series of chiral azacyclic nucleosides with four continuous stereocenters were obtained in 86-99% yields, >20:1 dr, and 94 → 99% ee via the Cu(I)-catalyzed asymmetric [3 + 2] cycloaddition. Both (E)- and (Z)-9-(2-tosylvinyl)-9H-purines were suitable dipolarophiles, enriching the structure diversity of azacyclic nucleosides. Furthermore, when α-methyl imino ester was explored, the corresponding azacyclic nucleoside with a chiral quaternary stereocenter could also be afforded with excellent results. (Chemical Equation Presented).

Discovery of inhibitors of the wnt and hedgehog signaling pathways through the catalytic enantioselective synthesis of an iridoid-inspired compound collection

Cousins you can count on: An iridoid-inspired compound collection was synthesized efficiently by the resolution of cyclic enones in an asymmetric cycloaddition with azomethine ylides. The collection contained novel potent inhibitors of the Wnt and Hedgehog signaling pathways. Copyright

Facile synthesis of chiral [2,3]-fused hydrobenzofuran: Via asymmetric Cu(i)-catalyzed dearomative 1,3-dipolar cycloaddition

Intermolecular asymmetric dearomative 1,3-dipolar cycloaddition of 2-nitrobenzofurans with azomethine ylides was enabled by using a chiral Cu(i)/(S,Sp)-iPr-Phosferrox catalyst. As a result, a series of highly stereoselective chiral [2,3]-fused hydrobenzofurans possessing four contiguous stereogenic centers were obtained with good to high yields, diastereoselectivities and enantioselectivities. The reaction has broad substrate scope tolerating various functional groups.

Copper/GanPhos-Catalyzed 1,3-Dipolar Cycloaddition of Azo?-methine Ylides: An Efficient Access to Chiral Pyrrolidine Spirocycles

A highly efficient copper/GanPhos-catalyzed 1,3-dipolar cyclo?-addition?-of azomethine ylides is reported. This viable transformation provides a series of optically active spiro[dihydronaphthalene-2,3′-pyrrolidine]s, bearing one spiro quaternary and three tertiary stereogenic centers, in good yields and with high ee values. This protocol features high diastereo- A nd enantioselectivity, broad substrate scope and mild reaction conditions.

Copper(i)/Ganphos catalysis: enantioselective synthesis of diverse spirooxindoles using iminoesters and alkyl substituted methyleneindolinones

A copper-catalyzed asymmetric 1,3-dipolar cycloaddition of glycine iminoesters with alkyl substituted 3-methylene-2-oxindoles is described. By usingde novodesign of P-stereogenic phosphines as ligands, spiro[pyrrolidin-3,3'-oxindole]s are generated in good to excellent yields with high asymmetric induction. A further reduced catalyst loading of 0.1 mol% is sufficient to achieve a satisfactory enantioselectivity of 90% ee. The DFT calculations suggest the second Michael addition of the 1,3-dipole to be the rate- andenantio-determining step. A key feature of this 1,3-dipolar cycloaddition is the wide substrate applicability, even with alkyl aldehyde-derived azomethine ylide; thus it has streamlined a highly enantioselective access to a new class of antiproliferative agents, MDM2-p53.

Well-Designed Phosphine-Urea Ligand for Highly Diastereo- and Enantioselective 1,3-Dipolar Cycloaddition of Methacrylonitrile: A Combined Experimental and Theoretical Study

A novel chiral phosphine-urea bifunctional ligand has been developed for Cu-catalyzed asymmetric 1,3-dipolar cycloaddition of iminoesters with methacrylonitrile, a long-standing challenging substrate in asymmetric catalysis. Distortion-interaction energy analysis based on density functional theory (DFT) calculations reveals that the distortion energy plays an important role in the observed enantioselectivity, which can be attributed to the steric effect between the phosphine ligand and the dipole reactant. DFT calculations also indicate that nucleophilic addition is the enantioselectivity-determining step and hydrogen bonding between the urea moiety and methacrylonitrile assists in control of the diastereo- and enantioselectivity. By a combination of metal catalysis and organocatalysis, excellent diastereo- and enantioselectivities (up to 99:1 diastereomeric ratio, 99% enantiomeric excess) as well as good yields are achieved. A wide range of substitution patterns of both iminoester and acrylonitrile is tolerated by this catalyst system, providing access to a series of highly substituted chiral cyanopyrrolidines with up to two quaternary stereogenic centers. The synthetic utility is demonstrated by enantioselective synthesis of antitumor agent ETP69 with a pivotal nitrile pharmacophore and an all-carbon quaternary stereogenic center.

Application of the Cu(i)/TEMPO/O2 catalytic system for aerobic oxidative dehydrogenative aromatization of pyrrolidines

A Cu(i)/TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy)-catalyzed aerobic oxidative dehydrogenative aromatization reaction of fully saturated pyrrolidines to synthesize multi-substituted pyrroles was developed for the first time. The use of a non-precious metal catalyst, green oxidant and environmentally friendly solvent made the reaction more sustainable.

Ligand-Controlled Inversion of Diastereo- and Enantioselectivity in Silver-Catalyzed Azomethine Ylide-Imine Cycloaddition of Glycine Aldimino Esters with Imines

A highly diastereo- and enantioselective silver-catalyzed azomethine ylide-imine (AYI) cycloaddition reaction of glycine aldimino esters with imines was developed in which the Xing-Phos-controlled syn-selective or DTBM-Segphos-induced anti-selective AYI cycloaddition reaction could be applied to the synthesis of a variety of stereodivergent 1-alkyl-2,5-substituted imidazolidines with high yields and excellent enantioselectivities (up to 99% ee) as well as good diastereoselectivities (up to 99:1 dr) under mild reaction conditions.