144465-16-7

Upstream product

• 5927-18-4 trimethyl phosphonoacetate 
• 99-90-1 para-bromoacetophenone 
• 623-43-8 crotonic acid methyl ester 
• 5467-74-3 4-Bromophenylboronic acid 
• 80-62-6 methacrylic acid methyl ester 
• 92846-10-1 tert-butyl 2-(4-bromophenyl)diazene-1-carboxylate 

Downstream Products

• 87979-60-0 4-(4-bromophenyl)furan-2(5H)-one 
• 143704-80-7 methyl 4-bromo-3-(4-bromophenyl)-2-butenoate 
• 90772-57-9 (E)-3-(4-bromo-phenyl)but-2-enoic acid 
• 1354197-47-9 (E)-3-(4-bromophenyl)-1-phenylbut-2-en-1-one 
• 143704-86-3 4-(4-bromophenyl)-N-phenylpyrrolone 

Relevant academic research and scientific papers

Dramatic Effect of γ-Heteroatom Dienolate Substituents on Counterion Assisted Asymmetric Anionic Amino-Cope Reaction Cascades

We report a dramatic effect on product outcomes of the lithium ion enabled amino-Cope-like anionic asymmetric cascade when different γ-dienolate heteroatom substituents are employed. For dienolates with azide, thiomethyl, and trifluoromethylthiol substituents, a Mannich/amino-Cope/cyclization cascade ensues to form chiral cyclohexenone products with two new stereocenters in an anti-relationship. For fluoride-substituted nucleophiles, a Mannich/amino-Cope cascade proceeds to afford chiral acyclic products with two new stereocenters in a syn-relationship. Bromide- and chloride-substituted nucleophiles appear to proceed via the same pathway as the fluoride albeit with the added twist of a 3-exo-trig cyclization to yield chiral cyclopropane products with three stereocenters. When this same class of nucleophiles is substituted with a γ-nitro group, the Mannich-initiated cascade is now diverted to a β-lactam product instead of the amino-Cope pathway. These anionic asymmetric cascades are solvent- and counterion-dependent, with a lithium counterion being essential in combination with etheral solvents such as MTBE and CPME. By altering the geometry of the imine double bond from E to Z, the configurations at the R1 and X stereocenters are flipped. Mechanistic, computational, substituent, and counterion studies suggest that these cascades proceed via a common Mannich-product intermediate, which then proceeds via either a chair (X = N3, SMe, or SCF3) or boat-like (X = F, Cl, or Br) transition state to afford amino-Cope-like products or β-lactam in the case of X = NO2.

Dihydropyridine compound and application thereof to drugs

The invention relates to a dihydropyridine compound and application of the dihydropyridine compound serving as a drug, in particular to application of the dihydropyridine compound serving as a drug for treating and preventing hepatitis B. Specifically, the invention relates to the compound shown as the general formula (I) or (Ia) (please see the specifications for the general formula (I) or (Ia))or stereoisomers, tautomer, a nitrogen oxide, solvate, metabolites and medically acceptable salt of the compound or a prodrug of the compound, wherein all variables are defined in the specification. The invention further relates to application of the compound shown as the general formula (I) or (Ia) or enantiomers, non-enantiomers, the tautomer, hydrates, the solvate or the medically acceptable salt of the compound serving as drugs, in particular to application of the compound or the enantiomers, the non-enantiomers, the tautomer, the hydrates, the solvate or the medically acceptable salt of the compound serving as the drugs for treating and preventing hepatitis B.

DMAP-Catalyzed [4 + 2] Cycloaddition of α,β-Unsaturated Carboxylic Acids with Ketones for Synthesis of α,β-Unsaturated δ-Lactones

The DMAP-catalyzed [4 + 2] cycloaddition of α,β-unsaturated carboxylic acids with ketones furnishing α,β-unsaturated δ-lactones in good yields (up to 80%) is described, which is the first example of remote γ-C(sp3)-H activation of α,β-unsaturated carboxylic acids facilitated by DMAP, a pyridine-based catalyst. Copyright

Highly efficient synthesis of chiral aromatic ketones: Via Rh-catalyzed asymmetric hydrogenation of β,β-disubstituted enones

A succinct and efficient protocol was developed for the synthesis of chiral aromatic ketones via asymmetric hydrogenation of β,β-disubstituted enones with rhodium catalysts based on chiral bisphosphine thiourea ligands. A series of substrates (17 examples) was smoothly catalyzed to afford the corresponding chiral aromatic ketones in high conversions (>99%) with excellent enantioselectivities (up to 96% ee).

Hydrogen Peroxide Promoted Mizoroki-Heck Reactions of Phenyldiazenes with Acrylates, Acrylamides, and Styrenes

Mizoroki-Heck reactions, which are well-known for aryldiazonium salts and which have recently been described for arylhydrazines, have now been extended to phenyldiazenes. In situ generation of phenyldiazenes from azocarboxylates allowed clean and selective reactions with styrenes, acrylates, and acrylamides using palladium(II) acetate in the presence of silver(I) acetate or hydrogen peroxide as oxidant. Hydrogen peroxide was thereby shown to be a cheap and broadly applicable alternative for the established palladium-silver(I) system.

Rhodium-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carbonyl Compounds via Thiourea Hydrogen Bonding

The strategy of secondary interaction enables enantioselectivity for homogeneous hydrogenation. By introducing hydrogen bonding of substrates with thiourea from the ligand, α,β-unsaturated carbonyl compounds, such as amides and esters, are hydrogenated wi

Enantioselective Rh-catalyzed hydrogenation of 3-aryl-4-phosphonobutenoates with a P-stereogenic BoPhoz-type ligand

A series of chiral 3-aryl-4-phosphonobutyric acid esters were synthesized in high enantioselectivities (93-98% ee) via the Rh-catalyzed asymmetric hydrogenation of the corresponding 3-aryl-4-phosphonobutenoates using a P-stereogenic BoPhoz-type phosphine-aminophosphine ligand. The methodology has been successfully applied to the asymmetric synthesis of a potential GABA B antagonist, (R)-phaclofen, in high enantioselectivity.

Oxygen and base-free oxidative heck reactions of arylboronic acids with olefins

A mild and efficient protocol for palladium-catalyzed oxidative Heck reactions of arylboronic acids with both electron-rich and -deficient olefins is described. In contrast to the normal oxidative Heck coupling, this new method works in the absence of a base, oxygen, or other external oxidants. With a wide variety of substrates tolerated, the method broadens the scope of palladium-catalyzed coupling reactions. Copyright