Selective friedel crafts

To develop dearomatization reactions based on a nucleophilic activation of phenols, naphthols, and indoles, ipso-Friedel-Crafts-type C-alkylation must be selectively promoted over competitive O- or N-alkylation reactions. Resolving this chemoselectivity issue is essential for developing this class dearomatization reaction. We found that various dearomatization reactions could be developed using appropriately designed aromatic substrates with an electrophilic moiety for intramolecular reactions. This review describes the transition-metal-catalyzed dearomatization reactions developed by our group...

Bis(dithienylethene)-based BINOL-derived phosphoric acid (DTE-BPA) has been developed as a light-controlled chiral organocatalyst for the first time. The photoinduced modulation of the reactivity and selectivity via the open/close isomerization of the DTE scaffold led to superior light-controlled ability in the enantioselective aza-Friedel-Crafts reaction of aldimines with indoles. DFT studies showed that photoisomerization is accompanied by a shift of 1.1 p K a units between the open and closed isomers.

A first hexaphenylsilole-based conjugated microporous polymer, termed THPS, was prepared by a Friedel-Crafts arylation reaction of 1,1,2,3,4,5-hexabenylthirole with 2,4,6-trichloro-1,3,5-triazine catalyzed by anhydrous aluminium trichloride (AlCl3 ) in 1,2-dichloroethane. Its Brunauer-Emmett-Teller and Langmuir surface area reached up to 1579 and 2081 m2 g-1 , and total pore volume and micropore pore volume were severally 0.8325 and 0.7322 cm3 g-1 . THPS could fluorescence-sense o-nitrophenol with high sensitivity and selectivity...

In this work, for the first time, naphthalene (NA)-based polymers were synthesized by one-stage Friedel-Crafts crosslinking. The influence of NA functionalization by -OH, -SO3 H, and -NO2 groups on the polymers' porosity and distribution of the catalytically active phase (Pd) was studied. Synthesized catalytic systems containing 1 wt.% of Pd either in the form of Pd(II) species or Pd(0) nanoparticles supported on NA-based polymers were tested in a model reaction of Suzuki cross-coupling between 4-bromoanisole and phenylboronic acid under mild reaction conditions (60 °C, ethanol-water mixture as a solvent)...

A commercial zeolite is shown to be a highly effective heterogeneous catalyst for the Friedel-Crafts alkyation of mandelic acid with aromatic substrates. The reaction yields mixed diarylacetic acids in one step avoiding the need for inert atmosphere techniques or superacids. The observed reaction pathways are zeolite framework dependent with only the FAU framework giving very high selectivity to the mixed diarylacetic acids.

In this study, we developed an organocatalyst-controlled site-selectivity switchable Friedel-Crafts reaction of 1-naphthols and 2,3-dioxopyrrolidines. The o -selective Friedel-Crafts reaction was achieved with chiral tertiary amines, while the p -selective Friedel-Crafts reaction was accomplished with Brønsted acids or Lewis acids. With this protocol, a range of functionalized polycyclic 2-pyrrolidinone derivatives were prepared. Moreover, theoretical mechanistic investigations provided insights into the site-selectivity reaction pathway and the origin of chiral induction for the o -selective Friedel-Crafts reaction...

Friedel-Crafts acylation of dipyrromethane with cinnamoyl chloride was conducted to obtain dicinnamoyl dipyrromethane compounds 3 and 4. Both compounds were subsequently oxidized by DDQ to produce dicinnamoyl dipyrromethene ligands (DC-1 and Dc-2). A large bathochromic shift compared to dipyromethene (D) was observed at 95 nm for DC-1 and 67 nm for DC-2. Both compounds showed remarkable chelation-enhanced fluorescence (CHEF) upon addition of zinc(II) ions. Similar to the quadrupolar system, DC-1 exhibited absorption and emission near the optical windows of the tissue...

A catalyst-controlled divergent synthesis of bridged [3.3.1] bis(indolyl)-oxanes and cis -[6.7] fused bis(indolyl) oxepanes via diastereoselective desymmetrization of bis(indolyl)-cyclohexadienones is presented for the first time. The reaction is highly atom- and step-economic, furnishing sp3 -rich functionalized bis(indolyl) derivatives in good to excellent yields with wide substrate scope. The reaction proceeds through Friedel-Crafts alkylation followed by catalyst-controlled selective C-C bond formation/rearrangement...

Carbon-fluorine bonds are stable and have demonstrated sluggishness against various chemical manipulations. However, selective transformations of C-F bonds can be achieved by developing appropriate conditions as useful synthetic methods in organic chemistry. This review focuses on C-C bond formation at monofluorinated sp3 -hybridized carbons via C-F bond cleavage, including cross-coupling and multi-component coupling reactions. The C-F bond cleavage mechanisms on the sp3 -hybridized carbon centers can be primarily categorized into three types: Lewis acids promoted F atom elimination to generate carbocation intermediates; nucleophilic substitution with metal or carbon nucleophiles supported by the activation of C-F bonds by coordination of Lewis acids; and the cleavage of C-F bonds via a single electron transfer...

Methyltransferases provide excellent specificity in late-stage alkylation of biomolecules. Their dependence on S -adenosyl-L-methionine (SAM) mandates efficient access to SAM analogues for biocatalytic applications. We directly compared halide methyltransferase (HMT) and methionine adenosyltransferase (MAT) to access SAM analogues and explored their utility in cascade reactions with NovO for regioselective, late-stage Friedel-Crafts alkylation of a coumarin. The HMT cascade efficiently provided SAM for methylation, while the MAT cascade also supplied high levels of SAM analogues for alkylation reactions...

Over the past decades, the advent of asymmetric organocatalysis has changed the way chemists think about creating or breaking chemical bonds, enabling new enantioselective strategies for functionalized molecules. The success of asymmetric organocatalysis is notably based on the existence of various activation modes, leading to countless transformations, and on the vast array of available chiral organic catalysts. Breakthroughs in this area have also been driven by selective functionalization of compounds with multiple activation sites such as cyclohexanone-derived dienones...

Silver is an important precious metal with superior ductility, electrical and thermal conductivity, photosensitivity, and antibacterial properties. However, without proper recycling and treatment, silver emissions may pose a threat to the human health and subsistence environment due to their toxicity. Therefore, it is environmentally and economically important to recover Ag from waste electronic equipment and anode slime. Herein, carboxyl functionalized modified magnetic nanoparticles (Fe3 O4 @3-phenylglutaricacid nanoparticles) were designed and prepared to obtain the low-cost magnetic pitch-based HCP adsorbents (MPHCP and P-MPHCP)...

Direct para-selective C(sp2 )-H alkylation of electron-deficient arenes based on the electroreduction-enabled radical addition of alkyl bromides has been developed under mild conditions. In the absence of any metals and redox agents, the simple electrolysis system tolerates a variety of primary, secondary, and tertiary alkyl bromides and behaves as an important complement to the directed alkylation of the C(sp2 )-H bond and the classic Friedel-Crafts alkylation. This electroreduction process provides a more straightforward, environmentally benign, and effective alkylation method for electron-deficient arenes...

An efficient and straightforward approach for the synthesis of C7 site-selective BINOL derivatives has been achieved via cost-effective Co(III)-catalyzed C-H cascade alkenylation/intramolecular Friedel-Crafts alkylation of BINOL units and propargyl cycloalkanols. Under the advantage of the pyrazole directing group, the protocol allows the rapid synthesis of various BINOL-tethered spiro[cyclobutane-1,1'-indenes].

σ-Lewis base-catalyzed regio- and enantioselective aza-Morita-Baylis-Hillman (MBH) reaction of α,β,γ,δ-unsaturated systems remains a challenge due to the intrinsic covalent activation mode. Here we demonstrate that a Pd0 complex can mediate the dehydrogenative reaction of γ,δ-unsaturated compounds to give corresponding electron-poor dienes, which further undergo δ-regioselective umpolung Friedel-Crafts-type addition to imines via auto-tandem Pd0-π-Lewis base catalysis...

A facile and efficient synthetic method for the construction of C3-hydroxyalkylated imidazo[1,2- a ]pyridines and indoles by a Zn(OTf)2 -catalyzed Friedel-Crafts hydroxyalkylation of imidazo[1,2- a ]pyridines and indoles with carbonyl compounds under mechanochemical conditions is reported. Good product selectivity, shorter reaction time, ambient reaction temperature, tolerance of a wide range of functional groups, broad substrate scope, moderate to good yield of products, and scalability are the salient features of the developed methodology...

A molecularly imprinted hypercrosslinked polymer (HCP) was synthesized from the polymerization of mesitylene monomer, terephthaloyl chloride crosslinker, and tannic acid (TA) template through FeCl3 -catalyzed Friedel-Crafts acylation. The TA-imprinted HCP (TAHCP) was capable of IUPAC Type I mesoporosity, with specific surface area of 1258 m2 g-1 , monolayer adsorption capacity of 289 cm2 g-1 , pore sizes ranging from 4.4 to 12.6 Å, amorphous morphology, and characteristic absorption and emission bands...

The discovery of a series of coupling reactions between various building blocks has driven the development of porous organic polymers, but the common usage of expensive and air-sensitive organometallic catalysts and complex procedures in harsh syntheses has limited their expansion. A microporous hypercrosslinked polymer (HCP) was synthesized by polymerizing a naphthalene monomer and a 1,4-dimethoxybenzene crosslinker using Friedel-Crafts alkylation over an FeCl3 catalyst and imprinted with 3,5-dinitrosalicylic acid (DNS)...

In this work, Friedel-Crafts alkylation was successfully applied to prepare a magnetic ionic liquid hypercrosslinked polymer composite (Fe3 O4 @IL-HCP), which was subsequently employed as magnetic solid-phase extraction (MSPE) adsorbent for the isolation and enrichment of trace non-steroidal anti-inflammatory drugs (NSAIDs). The developed composite was comprehensively characterized using various techniques, with the results indicating that it possessed high saturation magnetization (39.44 em g -  1 ), large specific surface area (175 m2 g -  1 ), and high adsorption capacity for NSAIDs...

Pore environment modulation with high-density polarizing groups in metal-organic frameworks (MOFs) can effectively accomplish selective and multicyclic carbon dioxide (CO2 ) adsorption, whereas the incorporation of task-specific organic sites inside these porous vessels promise to evade self-quenching, solubility, and recyclability issues in hydrogen-bond donating (HBD) catalysis. However, concurrent amalgamation of both these attributes over a single platform is rare but extremely demanding in view of sustainable applications...