86170-45-8

Upstream product

• 625-38-7 but-3-enoic acid 
• 100-51-6 benzyl alcohol 
• 81867-37-0 benzyl iodoacetate 
• 625-35-4 trans-chrotonyl chloride 
• 54322-10-0 glutaric acid monobenzyl ester 
• 81927-55-1 O-benzyl 2,2,2-trichloroacetimidate 
• 593-60-2 Vinyl bromide 
• 124-38-9 carbon dioxide 
• 72824-04-5 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 100-44-7 benzyl chloride 
• 24850-33-7 allyltributylstanane 
• 105623-17-4 (Z)-N-(2-methylpropylidene)benzylamine N-oxide 
• 187661-86-5 buta-2,3-dienoic acid benzyl ester 
• 109-99-9 tetrahydrofuran 

Relevant academic research and scientific papers

ARYLAMIDES AND METHODS OF USE THEREOF

The present disclosure relates to heterocyclic compounds, pharmaceutically acceptable salts thereof, and pharmaceutical preparations thereof. Also described herein are compositions and the use of such compounds in methods of treating diseases and conditions mediated by deficient CFTR activity, in particular cystic fibrosis.

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.

Stereoselective Total Synthesis of the Dimeric Naphthoquinonopyrano-?-lactone (-)-Crisamicin A: Introducing the Dimerization Site by a Late-Stage Hartwig Borylation

The first stereoselective total synthesis of the dimeric naphthoquinonopyrano-?-lactone (-)-crisamicin A was realized (13 steps, 5% overall yield). 1,4,5-Trimethoxynaphthalene, reached in five known steps, was brominated at C-3 to install a but-3-enoic ester by an ensuing Heck coupling. An asymmetric Sharpless dihydroxylation followed and gave a β-hydroxy-?-lactone with >99.9% ee. Its OH substituent and acetaldehyde established the dihydropyran ring in a completely diastereoselective oxa-Pictet-Spengler cyclization. The 2,3-fused anisole moiety allowed the C5-H bond under Hartwig's conditions to be borylated. This set the stage for engaging the resulting C5-B bond in an oxidative dimerization, which led to a binaphthohydroquinon-5-yl. The latter was advanced to synthetic crisamicin A by a double CAN oxidation (→ a binaphthoquinon-5-yl) and a double demethylation.

Alkene synthesis by photocatalytic chemoenzymatically compatible dehydrodecarboxylation of carboxylic acids and biomass

Direct conversion of renewable biomass and bioderived chemicals to valuable synthetic intermediates for organic synthesis and materials science applications by means of mild and chemoselective catalytic methods has largely remained elusive. Development of artificial catalytic systems that are compatible with enzymatic reactions provides a synergistic solution to this enduring challenge by leveraging previously unachievable reactivity and selectivity modes. We report herein a dual catalytic dehydrodecarboxylation reaction that is enabled by a crossover of the photoinduced acridine-catalyzed O-H hydrogen atom transfer (HAT) and cobaloxime-catalyzed C-H-HAT processes. The reaction produces a variety of alkenes from readily available carboxylic acids. The reaction can be embedded in a scalable triple-catalytic cooperative chemoenzymatic lipase-acridine-cobaloxime process that allows for direct conversion of plant oils and biomass to long-chain terminal alkenes, precursors to bioderived polymers.

1,5,7-Triazabicylodec-5-ene-promoted direct vinylogous aldol reaction for the synthesis of 3-hydroxy-2-oxoindole derivatives

A simple and efficient method has been developed for the synthesis of 3-hydroxy-2-oxoindole derivatives through a direct vinylogous aldol reaction of allylic esters with isatins, catalyzed by 1,5,7-triazabicyclodec-5-ene. This method affords a variety of 3-hydroxy-2-oxoindole derivatives in moderate to excellent yields with high regioselectivities. An asymmetric version of this reaction catalyzed by Corey's chiral guanidine proceeded with moderate enantioselectivity. The protocol can also be used to synthesize isatin spiro ethers.

Synthesis of 2-Fluoroacetoacetic Acid and 4-Fluoro-3-hydroxybutyric Acid

The butyric acid scaffold is the base structure of several human metabolites that serve diverse and prominent biochemical roles including as oxidative sources of cellular energy and as substrates for biosynthesis. Derivatization of metabolites through incorporation of fluorine often alters bioactivity and can facilitate detection and analysis by nuclear magnetic resonance or positron emission tomography depending upon the fluorine isotope employed. We describe the synthesis of two new fluorinated butyric acids (and three related esters) that are derivatives of the metabolites acetoacetic acid and 3-hydroxybutyric acid. 4-Fluoro-3-hydroxybutyric acid is prepared from epoxy ester precursors via ring opening by triethylamine trihydrofluoride. 2-Fluoroacetoacetic acid is prepared by electrophilic fluorination of an acid-labile β-keto ester. The gradual pH-dependent decarboxylation of 2-fluoroacetoacetic acid is investigated by 19 F NMR spectroscopy.

Ester Formation via Symbiotic Activation Utilizing Trichloroacetimidate Electrophiles

Trichloroacetimidates are useful reagents for the synthesis of esters under mild conditions that do not require an exogenous promoter. These conditions avoid the undesired decomposition of substrates with sensitive functional groups that are often observed with the use of strong Lewis or Br?nsted acids. With heating, these reactions have been extended to benzyl esters without electron-donating groups. These inexpensive and convenient methods should find application in the formation of esters in complex substrates.

Remote Nucleophilic Allylation by Allylrhodium Chain Walking

Metal migration through a carbon chain is a versatile method for achieving remote functionalization. However, almost all known examples involve the overall net migration of alkylmetal species. Here, we report that allylrhodium species obtained from hydrorhodation of 1,3-dienes undergo chain walking toward esters, amides, or (hetero)arenes over distances of up to eight methylene units. The final, more highly conjugated allylrhodium species undergo nucleophilic allylation with aldehydes and with an imine to give Z-homoallylic alcohols and amines, respectively.

Carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacolborate catalyzed by palladium nanoparticles

Palladium-catalyzed carboxylative Suzuki coupling reactions of benzyl chlorides with allyl pinacolborate were successfully conducted in the absence of any extra ligand to produce β,γ-unsaturated esters in satisfactory to good yields. The carboxylative Suzuki coupling reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles generated in situ through the formation of a π-benzylpalladium chloride intermediate.

Preparation method of beta, gamma-unsaturated ester compound

The invention belongs to the technical field of pharmaceutical and chemical intermediates and related chemistry and relates to a preparation method of a beta, gamma-unsaturated ester compound. The preparation method is characterized in that transition metal palladium nano particles generated in situ are taken as a catalyst, carboxylation reaction among three components, namely a halogenated methyl(hetero)aromatic hydrocarbon compound, allyl boronic acid pinacol ester and carbon dioxide, is realized, and the unsaturated ester compound is generated. The unsaturated ester compound is an important chemical intermediate and can be used for synthesizing multiple extremely useful compounds. The preparation method is simple and convenient to operate, available in raw materials and environment-friendly and has important significance on application research of carbon dioxide.