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Synthesis of enones, pyrazolines and pyrrolines with gem-difluoroalkyl side chains.

ABSTRACT: Starting from easily accessible gem-difluoropropargylic derivatives, a DBU-mediated isomerisation affords enones in fair yields with a gem-difluoroalkyl chain. These derivatives were used to prepare pyrazolines and pyrrolines with the desired gem-difluoroalkyl side chain by cyclocondensations in good yields and with excellent stereoselectivity. A one-pot process was also successfully developed for these sequential reactions. By carrying out various types of Pd-catalyzed coupling reactions for compounds with a p-bromophenyl substituent a route to focused chemical libraries was demonstrated.

SUBMITTER: El Dine AN

PROVIDER: S-EPMC3817575 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

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Synthesis of enones, pyrazolines and pyrrolines with gem-difluoroalkyl side chains.

El Dine Assaad Nasr AN Khalaf Ali A Grée Danielle D Tasseau Olivier O Fares Fares F Jaber Nada N Lesot Philippe P Hachem Ali A Grée René R

Beilstein journal of organic chemistry 20130926

Starting from easily accessible gem-difluoropropargylic derivatives, a DBU-mediated isomerisation affords enones in fair yields with a gem-difluoroalkyl chain. These derivatives were used to prepare pyrazolines and pyrrolines with the desired gem-difluoroalkyl side chain by cyclocondensations in good yields and with excellent stereoselectivity. A one-pot process was also successfully developed for these sequential reactions. By carrying out various types of Pd-catalyzed coupling reactions for co ...[more]

PMID: 24204405

Similar Datasets

Chiral gem-difluoroalkyl reagents: gem-difluoroalkyl propargylic borons and gem-difluoroalkyl α-allenols† † Electronic supplementary information (ESI) available. CCDC 2246187. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc03266c

Project description:Chiral fluorinated reagents provide new opportunities for the discovery of drugs and functional materials because the introduction of a fluorinated group significantly alters a molecule's physicochemical properties. Chiral gem-difluoroalkyl fragments (R–CF2–C*) are key motifs in many drugs. However, the scarcity of synthetic methods and types of chiral gem-difluoroalkyl reagents limits the applications of these compounds. Herein, we report two types of chiral gem-difluoroalkyl reagents chiral gem-difluoroalkyl propargylic borons and gem-difluoroalkyl α-allenols and their synthesis by means of methods involving rhodium-catalyzed enantioselective B–H bond insertion reactions of carbenes and Lewis acid-promoted allenylation reactions. The mild, operationally simple method features a broad substrate scope and good functional group tolerance. These two types of reagents contain easily transformable boron and alkynyl or allenyl moieties and thus might facilitate rapid modular construction of chiral molecules containing chiral gem-difluoroalkyl fragments and might provide new opportunities for the discovery of chiral gem-difluoroalkyl drugs and other functional molecules. Two types of chiral gem-difluoroalkyl reagents, chiral gem-difluoroalkyl propargylic borons and gem-difluoroalkyl α-allenols were developed by means of Rh-catalyzed enantioselective B–H bond insertion and Lewis acid-promoted allenylation.

| S-EPMC10466307 | biostudies-literature

Preparation of imidazo[1,2-a]-N-heterocyclic derivatives with gem-difluorinated side chains.

Project description:Using an aerobic oxidative coupling, different new imidazo[1,2-a]-N-heterocycles with gem-difluroroalkyl side chains have been prepared in fair yields by the reaction of gem-difluoroenones with aminopyridines, -pyrimidines and -pyridazines. Condensed heterocycles of this type play an important role as key core structures of various bioactive compounds. Further, starting with a chloroimidazopyridazine derivative, Pd-catalyzed coupling reactions as well as nucleophilic substitutions have been performed successfully in order to increase the molecular diversity.

| S-EPMC5647726 | biostudies-literature

Asymmetric [2+1] cycloaddition of difluoroalkyl-substituted carbenes with alkenes under rhodium catalysis: Synthesis of chiral difluoroalkyl-substituted cyclopropanes.

Project description:Herein, we report a novel strategy for the synthesis of chiral difluoroalkyl-substituted cyclopropanes through enantioselective [2 + 1] cyclopropanation of alkenes and difluoroalkyl-substituted carbenes under rhodium catalysis, wherein the newly designed α, α-difluoro-β-carbonyl ketone N-triftosylhydrazones are used as the difluoroalkyl-substituted carbenes precursors. This approach represents the first asymmetric cyclopropanation of alkenes with difluoroalkyl carbenes, featuring high yield, high enantioselectivity, and broad substrate scope. Gram-scale synthesis and further interconversion of diverse functional groups demonstrate the usefulness of this protocol in the preparation of diverse functionalized chiral difluoroalkyl-substituted cyclopropanes.

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Synthesis of Novel Tetrahydroisoquinoline CXCR4 Antagonists with Rigidified Side-Chains.

Project description:A structure-activity relationship study of potent TIQ15-derived CXCR4 antagonists is reported. In this investigation, the TIQ15 side-chain was constrained to improve its drug properties. The cyclohexylamino congener 15a was found to be a potent CXCR4 inhibitor (IC50 = 33 nM in CXCL12-mediated Ca2+ flux) with enhanced stability in liver microsomes and reduced inhibition of CYP450 (2D6). The improved CXCR4 antagonist 15a has potential therapeutic application as a single agent or combinatory anticancer therapy.

| S-EPMC5807867 | biostudies-other

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains.

Project description:Recently, a renewable five-membered lactone containing citronellol (HBO-citro) was synthesized from levoglucosenone (LGO). A one-pot two-step pathway was then developed to produce a mixture of 5- and 6-membered Lactol-citro molecules (5ML and 6ML, respectively) from HBO-citro. Proton nuclear magnetic resonance (1H NMR) of a mixture of 5ML and 6ML at varying temperatures showed that the chemical shifts of the hydroxyls, as well as the 5ML:6ML ratio, are temperature-dependent. Indeed, a high temperature, such as 65 °C, led to an up-field shielding of the hydroxyl protons as well as a drop in the 5ML:6ML ratio. The monomers 5ML and 6ML were then engaged in polycondensation reactions involving diacyl chlorides. Renewable copolyesters with low glass transition temperatures (as low as -67 °C) and cross-linked citronellol chains were prepared. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG). A higher degradation rate was found for the polymers prepared using Lactol-citro molecules, compared to those obtained by the polycondensation reactions of diacyl chlorides with Triol-citro-a monomer recently obtained by the selective reduction of HBO-citro.

| S-EPMC9146931 | biostudies-literature

Synthesis and Telomeric G-Quadruplex-Stabilizing Ability of Macrocyclic Hexaoxazoles Bearing Three Side Chains.

Project description:G-quadruplexes (G4s), which are structures formed in guanine-rich regions of DNA, are involved in a variety of significant biological functions, and therefore "sequence-dependent" selective G4-stabilizing agents are required as tools to investigate and modulate these functions. Here, we describe the synthesis of a new series of macrocyclic hexaoxazole-type G4 ligand (6OTD) bearing three side chains. One of these ligands, 5b, stabilizes telomeric G4 preferentially over the G4-forming DNA sequences of c-kit and K-ras, due to the interaction of its piperazinylalkyl side chain with the groove of telomeric G4.

| S-EPMC6358838 | biostudies-literature

Using automated synthesis to understand the role of side chains on molecular charge transport.

Project description:The development of next-generation organic electronic materials critically relies on understanding structure-function relationships in conjugated polymers. However, unlocking the full potential of organic materials requires access to their vast chemical space while efficiently managing the large synthetic workload to survey new materials. In this work, we use automated synthesis to prepare a library of conjugated oligomers with systematically varied side chain composition followed by single-molecule characterization of charge transport. Our results show that molecular junctions with long alkyl side chains exhibit a concentration-dependent bimodal conductance with an unexpectedly high conductance state that arises due to surface adsorption and backbone planarization, which is supported by a series of control experiments using asymmetric, planarized, and sterically hindered molecules. Density functional theory simulations and experiments using different anchors and alkoxy side chains highlight the role of side chain chemistry on charge transport. Overall, this work opens new avenues for using automated synthesis for the development and understanding of organic electronic materials.

| S-EPMC9019014 | biostudies-literature

Synthesis and drag reduction properties of a hydrophobically associative polymer containing ultra-long side chains.

Project description:Different from common hydrophobic associative polymers, a new hydrophobic associative polyacrylamide (HAPAM) with ultra-long side chains was synthesized and aimed to be used as drag reducer in this work. Firstly, a water-soluble hydrophobic monomer (named AT114) was obtained by alcoholysis reaction with acryloyl chloride and triton 114, then the drag reducer was obtained by radical copolymerization of AM, AMPS and AT114. The structures of AT114 and drag reducer were characterized by IR and NMR. Slick water was obtained by dissolving a small amount drag reducer in water. Although the viscosity of slick water varied greatly in fresh water and brine, the drag reduction rate always remained at a high level when flowing in pipelines. When the concentration of the drag reducer was 0.03% in fresh water, drag reduction rate can be up to 76.7%, while in high concentration brine, still as high as 76.2%. It shows that salt has no obvious negative impact on the drag reduction rate. That is also to say, in the case of low viscosity, the viscosity change has no obvious impact on drag reduction rate. From the Cryo-TEM observation, it can be concluded that the drag reducer forms sparse network structures in water, which is the direct reason for drag reducing effect. This finding provides knowledge regarding the development of new drag reducers.

| S-EPMC10240801 | biostudies-literature

Synthesis and Catalytic Activity of Amino Acids and Metallopeptides with Catalytically Active Metallocyclic Side Chains.

Project description:Two approaches to prepare amino acids with catalytically active organometallic side chains are presented. These methods are notable in that they provide access either free or N-protected compounds that are structurally analogous to naturally occurring amino acids. The N-protected organo-metallic amino acids are compatible with standard peptide coupling conditions and can be used to prepare catalytically active metallopeptides.

| S-EPMC3614014 | biostudies-literature

Hydroxyproline-derived pseudoenantiomeric [2.2.1] bicyclic phosphines: asymmetric synthesis of (+)- and (-)-pyrrolines.

Project description:We have prepared two new diastereoisomeric 2-aza-5-phosphabicyclo[2.2.1]heptanes from naturally occurring trans-4-hydroxy-L-proline in six chemical operations. These syntheses are concise and highly efficient, with straightforward purification. When we used these chiral phosphines as catalysts for reactions of γ-substituted allenoates with imines, we obtained enantiomerically enriched pyrrolines in good yields with excellent enantioselectivities. These two diastereoisomeric phosphines functioned as pseudoenantiomers, providing their chiral pyrrolines with opposite absolute configurations.

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