60754-33-8

Upstream product

• 78-40-0 triethyl phosphate 
• 2417-93-8 propyllithium 
• 100-52-7 benzaldehyde 
• 105-58-8 Diethyl carbonate 
• 18812-51-6 diethyl propylphosphonate 
• 533-68-6 2-bromobutyric acid ethyl ester 
• 75-24-1 trimethylaluminum 
• 124778-94-5 ethyl 2-(chloromethyl)-3-phenyl-(Z)-2-propenoate 
• 17145-91-4 triethyl 2-ethylphosphonoacetate 
• 105479-98-9 ethyl 2-(acetoxy(phenyl)methyl)acrylate 
• 74-88-4 methyl iodide 
• 7693-31-4 α-chlorobenzyl phenyl sulfide 
• 831-91-4 Benzyl phenyl sulfide 
• 105-54-4 butanoic acid ethyl ester 

Downstream Products

• 3571-78-6 2,4-Dioxo-5-ethyl-6-phenyl-tetrahydro-1,3-thiazin 
• 1408163-11-0 (S)-ethyl 2-benzylbutanoate 
• 2983-36-0 ethyl 2-benzylbutanoate 
• 56407-97-7 (E)-2-benzylidenebutan-1-ol 
• 26197-64-8 (E)-2-benzylidenebutanoic acid 

Relevant academic research and scientific papers

Copper-Photocatalyzed Contra-Thermodynamic Isomerization of Polarized Alkenes

The contra-thermodynamic isomerization of α- and β-substituted cinnamate derivatives catalyzed by the Cu(OAc)2/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E → Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good to excellent ratios. The mechanism of this process based on the transient formation of a chromophore was also studied.

Asymmetric Nazarov Cyclizations of Unactivated Dienones by Hydrogen-Bond-Donor/Lewis Acid Co–Catalyzed, Enantioselective Proton-Transfer

We report an enantioselective Nazarov cyclization catalyzed by chiral hydrogen-bond-donors in concert with silyl Lewis acids. The developed transformation provides access to tri-substituted cyclopentenones in high levels of enantioselectivity (up to 95% e.e.) from a variety of simple unactivated dienones. Kinetic and mechanistic studies are consistent with a reversible 4π-electrocyclization C?C bond-forming step followed by rate- and enantio-determining proton-transfer as the mode of catalysis. (Figure presented.).

Dianionic Phase-Transfer Catalyst for Asymmetric Fluoro-cyclization

Inspired by the dicationic nature of the electrophilic fluorinating reagent, Selectfluor (1), we rationally designed a series of dicarboxylic acid precatalysts (2), which, when deprotonated, act as anionic phase-transfer catalysts for asymmetric fluorination of alkenes. Among them, 2a having the shortest linker moiety efficiently catalyzed unprecedented 6-endo-fluoro-cyclization of various allylic amides, affording fluorinated dihydrooxazine compounds with high enantioselectivity (up to 99% ee). In addition to cyclic substrates, acyclic trisubstituted alkenes underwent the reaction with good diastereoselectivity, whereas low diastereoselectivity was observed for linear disubstituted alkenes. Results suggest that the reaction proceeds via a fluoro-carbocation intermediate.

Highly enantioselective iridium-catalyzed hydrogenation of α,β-unsaturated esters

α,β-Unsaturated esters have been employed as substrates in iridium-catalyzed asymmetric hydrogenation. Full conversions and good to excellent enantioselectivities (up to 99 % ee) were obtained for a broad range of substrates with both aromatic- and aliphatic substituents on the prochiral carbon. The hydrogenated products are highly useful as building blocks in the synthesis of a variety of natural products and pharmaceuticals. Asymmetric hydrogenation: A variety of α,β-unsaturated esters were hydrogenated with high enantioselectivities (see scheme). The hydrogenated products have been used in synthetic transformations as well as in formal total syntheses. Copyright

Mapping the mechanism of nickel-ferrophite catalysed methylation of baylis-hillman-derived SN2′ electrophiles

Enantioselective Ni-catalysed methylation of Baylis-Hillman-derived allylic electrophiles in the presence of ferrophite ligands has been investigated computationally and experimentally. The sense and degree of enantioselectivity attained is independent of both the leaving group and the isomeric structure of the initial allylic halide. DFT studies support the selective formation of a limited number of energetically favoured anti and syn π-allyl intermediates. The observed regio- and enantioselectivity can be rationalised based on the energetics of these structures.

1-alkoxycarbonylalkylidenetriphenylarsoranes: Preparation and reactions

The higher homologues of the well-studied alkoxycarbonylmethylenetriphenylarsonium ylide (3, R=H) can be easily obtained through the sequence: a), preparation of alkyl 2-trifloxyalkanoates (1); b), reaction between these trifloxyderivatives and triphenylphosphine to give 1-alkoxycarbonylalkyltriphenylarsonium triflates (2); and c), basic treatment of the triphenylarsonium triflates (2) with alumina-supported potassium fluoride to give 1-alkoxycarbonylalkyledenetriphenylarsonium ylides (3). These higher homologues of (3, R=H) react with aromatic aldehydes in good to excellent yields, and give rise to synthetically interesting 'coupling' and cyclopropanation reactions.

Applications of the Baylis-Hillman Reaction 2: a Simple Stereoselective Synthesis of (E)- and (Z)-Trisubstituted Alkenes

Reaction of Grignard reagents with methyl 3-acetoxy-2-methylenealkanoates produces (2E)-2-substituted alk-2-enoates, whereas a similar reaction with 3-acetoxy-2-methylenealkanenitriles provides (2Z)-2-substituted alk-2-enenitriles in high (Z)-stereoselectivity.

Studies of the use of elemento-organic compounds of the fifteenth and sixteenth groups in organic synthesis LXXI. Reaction of α-halogeno carboxylic derivatives with carbonyl compounds promoted by tributylstibine

α,β-Unsaturated esters and amides were conveniently obtained from the trialkylstibine-promoted reaction of α-halogenocarboxylic derivatives with carbonyl compounds.In this reaction, a quaternary stibonium salt is an active intermediate that can be trapped and can undergo further reaction with the substrate.

α-LITHIOALKYLPHOSPHONATES AS FUNCTIONAL GROUP CARRIERS. AN IN SITU ACRYLIC ESTER SYNTHESIS

Condensation of α-lithioalkylphosphonates with diethylcarbonate in the presence of LDA generates carbethoxyalkylphosphonate anions which upon treatment at room temperature with aldehydes constitutes an in situ acrylic ester synthesis.