127404-66-4

Upstream product

• 1117-71-1 methyl 4-bromocrotonate 
• 17151-47-2 tributyl(4-fluorophenyl)stannane 
• 107-93-7 (E)-but-2-enoic acid 
• 352-34-1 4-fluoro-1-iodobenzene 
• 459-57-4 4-fluorobenzaldehyde 
• 36626-29-6 (2-carboxyethyl)triphenylphosphonium chloride 
• 141-82-2 malonic acid 
• 1736-67-0 4-fluorophenylacetaldehyde 
• 349-88-2 4-Fluorobenzenesulfonyl chloride 
• 625-38-7 but-3-enoic acid 
• 2266-41-3 4-fluorobenzenesulfonylhydrazide 
• 124-38-9 carbon dioxide 
• 27064-92-2 1-(3-chloro-1-propen-1-yl)-4-fluorobenzene 
• 64-18-6 formic acid 

Downstream Products

• 589-06-0 4-(4-fluorophenyl)butanoic acid 
• 703-67-3 6-fluoro-3,4-dihydronaphthalen-1(2H)-one 

Relevant academic research and scientific papers

A novel phenylsulfenylation of unsaturated acids or alcohols by methyl phenyl sulfoxide and substoichiometric (COCl)2

Phenylsulfenylation of unsaturated acids and alcohols has been achieved by methyl phenyl sulfoxide (PhSOCH3) and substoichiometric (COCl)2 in CH3CN. The corresponding cyclization products, lactones with a phenylthio group from unsaturated acids were obtained in mediate to good yields, whereas the cyclic ethers with a phenylthio group from unsaturated alcohols in relatively low yields. PhSOH was proposed to be the key active species for phenylsulfenylation, which was generated in situ by the reaction of PhSOCH3 with substiochiometric amount of (COCl)2. Anhydrous HCl could replace (COCl)2 in the reactions to give the comparable results.

Synthesis of Enantiopure ω-(4-Fluorophenyl)-6,11-Methylene Lipoxin B 4Methyl Ester

The synthesis of Lipoxin B 4analogues (LXB 4) to gain access to stabilized inflammation-resolving compounds is an active field of research. Focusing on variation and stabilization of the conjugated E, Z, E, E C6-C13 tetraene moiety of natural LXB 4, a methylene bridge introduced between C6 and C11 suppresses any Z / E isomerization of the C8-C9 olefin. Furthermore, rapid ω-oxidation (C20) should be avoided by replacing the C18-C20 segment by an aromatic moiety. Optically active C1-C12 building blocks were accessed from methyl cycloheptatriene-1-carboxylate (C6-C11, C21) and glutaryl chloride (C1-C5) as described earlier. The ω-segment was generated via a five-step sequence starting from 4-arylbutanoic acid. Horner key olefination enabled assembly of the carbon backbone. A final five-step sequence including a chelate Cram reduction of the unsaturated ketone moiety afforded the target ω-aryl 6,11-methylene-LXB 4methyl ester.

Palladium-Catalyzed Direct C-H Arylation of 3-Butenoic Acid Derivatives

We report herein a direct method to synthesize 4-aryl-3-butenoic acid through a carboxylic-acid-directed oxidative Heck reaction. The various 4-aryl-3-butenoic acids are easily prepared in moderate to good yields. In view of the promising bioactivity of 4-phenyl-3-butenoic acid previously reported, its derivatives reported here may be bioactive.

Electroreductive Cobalt-Catalyzed Carboxylation: Cross-Electrophile Electrocoupling with Atmospheric CO2

The chemical use of CO2 as an inexpensive, nontoxic C1 synthon is of utmost topical interest in the context of carbon capture and utilization (CCU). We present the merger of cobalt catalysis and electrochemical synthesis for mild catalytic carb

Intramolecular Cyclization of Vinyldiazoacetates as a Versatile Route to Substituted Pyrazoles

Vinyldiazo compounds undergo a thermal electrocyclization to form pyrazoles in yields of up to 95percent. The reactions are operationally simple, use readily available starting materials, require no intervention of a catalyst, and enable the synthesis of mono-, di- A nd tri-substituted pyrazoles. With the ability to produce highly substituted pyrazoles and the flexibility in installing various types of substituents, this method constitutes a new entry to this valuable heterocyclic scaffold and may be of interest to all branches of the chemical industry.

An Enzymatic Platform for the Highly Enantioselective and Stereodivergent Construction of Cyclopropyl-δ-lactones

Abiological enzymes offers new opportunities for sustainable chemistry. Herein, we report the development of biological catalysts derived from sperm whale myoglobin that exploit a carbene transfer mechanism for the asymmetric synthesis of cyclopropane-fused-δ-lactones, which are key structural motifs found in many biologically active natural products. While hemin, wild-type myoglobin, and other hemoproteins are unable to catalyze this reaction, the myoglobin scaffold could be remodeled by protein engineering to permit the intramolecular cyclopropanation of a broad spectrum of homoallylic diazoacetate substrates in high yields and with up to 99 % enantiomeric excess. Via an alternate evolutionary trajectory, a stereodivergent biocatalyst was also obtained for affording mirror-image forms of the desired bicyclic products. In combination with whole-cell transformations, the myoglobin-based biocatalyst was used for the asymmetric construction of a cyclopropyl-δ-lactone scaffold at a gram scale, which could be further elaborated to furnish a variety of enantiopure trisubstituted cyclopropanes.

Synthesis of Allylboranes via Cu(I)-Catalyzed B-H Insertion of Vinyldiazoacetates into Phosphine-Borane Adducts

Cu(I) catalysts enable C-B bond formation via direct insertion of vinyldiazoacetates into B-H bonds of borane-phosphine Lewis adducts to form phosphine-protected allylboranes under mild conditions. The resulting allylborane-phosphine Lewis adducts can be used in the diastereoselective allylation of aldehydes directly without the need for removal of the phosphine. The allylation reaction proceeds with high diastereoselectivity and yields 5,6-disubstituted dihydropyranones after treatment with an appropriate acid.

Direct Enantioselective and Regioselective Alkylation of β,γ-Unsaturated Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

Efficient asymmetric alkylation of β,γ-unsaturated carboxylic acids without prior functionalization is enabled by chiral lithium amides. Enantioselectivity is imparted by a putative mixed lithium amide-enediolate aggregate that acts a traceless auxiliary formed in situ, allowing for a direct asymmetric alkylation and a simple recovery of the chiral reagent.

Stereoselective Ring-Opening of gem-Difluorocyclopropanes: An Entry to Stereo-defined (E,E)- and (E,Z)-Conjugated Fluorodienes

The ring-opening of gem-difluorocyclopropyl acetaldehydes producing selectively (E,E)- and (E,Z)-conjugated fluorodienals is described. Two stereo-divergent methods are presented to access both stereoisomers from a common precursor, in high yield and selectivity. The mechanistic aspect of these transformations is discussed.

Direct palladium-catalyzed carbonylative transformation of allylic alcohols and related derivatives

A direct, palladium-catalyzed, carbonylative transformation of allylic alcohols for the synthesis of β,γ-unsaturated carboxylic acids has been developed. With formic acid as the CO source, various allylic alcohols were conveniently transformed into the corresponding β,γ-unsaturated carboxylic acids with excellent linear and (E)-selectivity. The reaction was performed under mild conditions; toxic CO gas manipulation and high-pressure equipment were avoided in this procedure.