61140-47-4

Upstream product

• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 1896-62-4 (E)-benzalacetone 
• 100-52-7 benzaldehyde 
• 5381-93-1 1-hydroxy-1-phenyl-3-butanone 
• 75-77-4 chloro-trimethyl-silane 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 16029-98-4 trimethylsilyl iodide 
• 66132-97-6 2-trimethylsilyl-4-phenyl-1-oxa-1,3-butadiene 
• 70775-39-2 dimethylsulfoxonium methylide 
• 20511-04-0 (E)-4-(4-bromophenyl)but-3-ene-2-one 
• 6674-22-2 1,8-diazabicyclo[5.4.0]undec-7-ene 

Downstream Products

• 84175-44-0 (E)-1-phenyl-5-(phenylthio)-1-penten-3-one 
• 110550-13-5 4-acetyl-3,5-diphenyl-cyclohexanone 
• 121682-02-8 5-methoxy-1-phenylpent-1-en-3-one 
• 1097633-89-0 C₁₅H₁₆O₃ 
• 75-09-2 dichloromethane 
• 1278589-36-8 4-Acetyl-3-(4-nitrophenyl)-5-phenylcyclohexanone 
• 627106-92-7 (4'R,7S,11S)-7-(2,2-dimethyl-1,3-dioxolan-4-yl)-3,3-dimethyl-11-phenyl-2,4-dioxaspiro[5.5]undecane-1,5,9-trione 
• 6704-83-2 3-oxo-5-phenyl-4-pentenonitrile 
• 112698-74-5 (E)-1-hydroxy-4-phenylbut-3-en-2-one 
• 137726-66-0 3-Phenyl-5-trimethylsilanyloxy-3,6-dihydro-pyridazine-1,2-dicarboxylic acid diethyl ester 
• 109916-03-2 8-Phenyl-hexahydro-naphthalene-1,6-dione 
• 127941-19-9 (E)-5-Benzyloxy-1-phenyl-pent-1-en-3-one 

Relevant academic research and scientific papers

Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates

Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.

Synthesis of 1-hydrocarbon substituted cyclopropyl silyl ketones

The synthesis of cyclopropyl silyl ketones possessing a hydrocarbon group at 1-position of three-membered ring was investigated. The reaction of sulfoxonium ylide with α,β-unsaturated acylsilanes derived from α,β-unsaturated aldehydes did not afford the desired acylsilane derivatives. Instead, the corresponding silyl enol ethers were yielded exclusively. On the other hand, the Corey-Chaykovsky cyclopropanation of α-substituted α,β-unsaturated aldehydes proceeded well to give 1-substituted cyclopropyl aldehydes. The silyl substitution of formyl proton in the obtained aldehydes via umpolung of carbonyl group afforded the target acylsilanes.

Highly Enantioselective [5 + 2] Annulations through Cooperative N-Heterocyclic Carbene (NHC) Organocatalysis and Palladium Catalysis

The highly enantioselective [5 + 2] annulation of enals with vinylethylene carbonates through a cooperative N-heterocyclic carbene (NHC)/Pd catalytic system is reported. The use of a bidentate phosphine ligand was crucial to prevent coordination of the NH

Synthesis of β-Amino-Substituted Enones by Addition of Substituted Methyl Enones to Sulfinimines: Application to the Total Synthesis of Alkaloids (+)-Lasubine II and (+)-241D and the Formal Total Synthesis of (-)-Lasubine i

Addition of silyl enol ethers obtained from substituted methyl enones to chiral sulfinimines afforded the β-amino-substituted enones with excellent selectivity. Utility of the obtained N-sulfinyl β-amino ketones possessing α,β-unsaturation is exemplified

Novel Benzo[a]quinolizidine Analogs Induce Cancer Cell Death through Paraptosis and Apoptosis

Paraptosis is nonapoptotic cell death characterized by massive endoplasmic reticulum (ER)- or mitochondria-derived vacuoles. Induction of paraptosis offers significant advantages for the treatment of chemotherapy-resistant tumors compared with anticancer drugs that rely on apoptosis. Because some natural alkaloids induce paraptotic cell death, a novel series of benzo[a]quinolizidine derivatives were synthesized, and their antiproliferative activity and ability to induce cytoplasmic vacuolation were analyzed. Structural optimization led to the identification of the potent compound 22b, which inhibited cancer cell proliferation in vitro and in vivo and profoundly facilitated paraptosis-like cell death and induced caspase-dependent apoptosis. Further investigation revealed that 22b-mediated vacuolation originated from persistent ER stress and upregulation of LC3B. Paraptosis induced by benzo[a]quinolizidine derivatives thus represents an alternative strategy for cancer chemotherapy.

Conversion of Simple Cyclohexanones into Catechols

A novel I2-catalyzed direct conversion of cyclohexanones to substituted catechols under mild and simple conditions has been described. This novel transformation is remarkable with the multiple oxygenation and dehydrogenative aromatization processes enabled just by using DMSO as the solvent, oxidant, and oxygen source. This metal-free and simple system demonstrates a versatile protocol for the synthesis of highly valuable substituted catechols and therefore streamlines the synthesis and modification of biologically important molecules for drug discovery.

Difluorohomologation of ketones

A method for the homologation of ketones with the CF2 fragment is described. The reaction involves silylation, room-temperature difluorocyclopropanation of silyl enol ethers, and selective ring opening of cyclopropanes under acidic conditions. The whole three-step sequence is conveniently performed in a one-pot mode.

Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates

Trialkylsilyl enol ethers are versatile intermediates often used as enolate surrogates for the synthesis of carbonyl compounds. Yet there are no reports of broadly applicable, catalytic methods for the synthesis of chiral silyl enol ethers carrying latent functionalities useful for synthetic operations beyond the many possible reactions of the silyl enol ether moiety itself. Here we report a general procedure for highly catalytic (substrate:catalyst ratio up to 1000:1) and enantioselective (92% to 98% major enantiomer) synthesis of such compounds bearing a vinyl group at a chiral carbon at the β-position. The reactions, run under ambient conditions, use trialkylsiloxy-1,3-dienes and ethylene (1 atm) as precursors and readily available (bis-phosphine)-cobalt(II) complexes as catalysts. The silyl enolates can be readily converted into novel enantiopure vinyl triflates, a class of highly versatile cross-coupling reagents, enabling the syntheses of other enantiomerically pure, stereodefined trisubstituted alkene intermediates not easily accessible by current methods. Examples of Kumada, Stille, and Suzuki coupling reactions are illustrated.

Stereoselective Synthesis of Highly Substituted Tetrahydrofurans through Diverted Carbene O-H Insertion Reaction

Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. Under mild conditions, the single-step process starts as a carbene O-H insertion reaction, but is diverted by an intramolecular aldol reaction. Gone astray: Copper- or rhodium-catalyzed reactions of diazocarbonyl compounds with β-hydroxyketones give highly substituted tetrahydrofurans with excellent diastereoselectivity. The single-step reaction proceeds under mild conditions, starting as a carbene O-H insertion reaction, but then diverting to an intramolecular aldol reaction.

Iridium-catalyzed enantioselective allylation of silyl enol ethers derived from ketones and α,β-unsaturated ketones

The unified Ir-catalyzed enantioselective allylic substitution reactions of silyl enol ethers derived from ketones and α,β-unsaturated ketones with branched, racemic allylic alcohols are described. This transformation is catalyzed by the Carreira system and proceeds without fluoride, and with high ee and b:l ratio. The synthetic utility of this method was illustrated by the concise enantioselective total synthesis of marine natural products calyxolane A, B and by the assignment of the absolute configuration of calyxolane A.