Cu(II)-Mediated Sulfonylation of (Hetero)arenes with TosMIC Using Monodentate Directing Groups.

Monodentate chelation-assisted direct ortho-C-H sulfonylation of (hetero)arenes using TosMIC as the novel sulfonylating reagent has been developed. A broad range of substrates, including indolines, indoles, 2-phenylpyridines, and others were well tolerated to afford the corresponding products in moderate to good yields. Mechanistic studies revealed that the sulfonyl radical might be involved. Inspired by the above discovery, preliminary para-C-H sulfonylation of naphthalene substrate was also successfully realized. The current protocol featured with cheap metal catalysis, good functional group compatibility, and operational convenience.

Amine-Imine Nickel Catalysts with Pendant O-Donor Groups for Ethylene (Co)Polymerization.

The introduction of a secondary interaction is an efficient strategy to modulate transition-metal-catalyzed ethylene (co)polymerization. In this contribution, O-donor groups were suspended on amine-imine ligands to synthesize a series of nickel complexes. By adjusting the interaction between the nickel metal center and the O-donor group on the ligands, these nickel complexes exhibited high activities for ethylene polymerization (up to 3.48 × 106 gPE·molNi-1·h-1) with high molecular weight up to 5.59 × 105 g·mol-1 and produced good polyethylene elastomers (strain recovery (SR) = 69-81%). In addition, these nickel complexes can catalyze the copolymerization of ethylene with vinyl acetic acid, 6-chloro-1-hexene, 10-undecylenic, 10-undecenoic acid, and 10-undecylenic alcohol to prepare the functionalized polyolefins.

Tailored Supramolecular Cage for Efficient Bio-Labeling.

Fluorescent chemosensors are powerful imaging tools used in a broad range of biomedical fields. However, the application of fluorescent dyes in bioimaging still remains challenging, with small Stokes shifts, interfering signals, background noise, and self-quenching on current microscope configurations. In this work, we reported a supramolecular cage (CA) by coordination-driven self-assembly of benzothiadiazole derivatives and Eu(OTf)3. The CA exhibited high fluorescence with a quantum yield (QY) of 38.57%, good photoluminescence (PL) stability, and a large Stokes shift (153 nm). Furthermore, the CCK-8 assay against U87 glioblastoma cells verified the low cytotoxicity of CA. We revealed that the designed probes could be used as U87 cells targeting bioimaging.

Copper-catalyzed regioselective C2-H chlorination of indoles with para-toluenesulfonyl chloride.

A copper-catalyzed, pyrimidine directed regioselective C-H chlorination of indoles with para-toluenesulfonyl chloride (TsCl) has been developed. The reactions proceeded smoothly in the presence of 20 mol% of Cu(OAc)2 as the catalyst and TsCl as the chlorine source, delivering C2-chlorinated indoles with structural diversity in moderate to excellent yields. Mechanistic studies suggested that single electron transfer (SET) from Cu(II) to TsCl accompanied by the release of the p-toluenesulfonyl radical and the related Cu(III)Cl species might be involved in the reactions.

Synthesis of a Tetrahedral Metal-Organic Supramolecular Cage with Dendritic Carbazole Arms.

In recent years, incredible endeavors have been devoted to the design and self-assembly of discrete metal-organic cages (MOCs) with expanding intricacy and functionality. The controlled synthesis of metal-organic supramolecular cages with large branched chains remains an interesting and challenging work in supramolecular chemistry. Herein, a tetrahedral metal-organic supramolecular cage (ZnII4L4) containing 12 dendritic carbazole arms is unprecedentedly constructed through coordination-driven subcomponent self-assembly and characterized in different ways. Interestingly, tetrahedral supramolecular Cage-1 exhibited the potential for aggregation-induced emission (AIE) performance and stimulus-responsive luminescence features, and it achieved color-tunable photoluminescence due to the introduction of dendritic carbazole arms. Crucially, owing to the great photophysical properties of Cage-1 in solution, Cage-1 was enabled to act as a fluorescent ink for the vapor-responsive recording and wiping of information.

NaOH-Mediated Direct Synthesis of Quinoxalines from o-Nitroanilines and Alcohols via a Hydrogen-Transfer Strategy.

A NaOH-mediated sustainable synthesis of functionalized quinoxalines is disclosed via redox condensation of o-nitroamines with diols and α-hydroxy ketones. Under optimized conditions, various o-nitroamines and alcohols are well tolerated to generate the desired products in 44-99% yields without transition metals and external redox additives.

Iron-Mediated Selective Sulfonylmethylation of Aniline Derivatives with p-Toluenesulfonylmethyl Isocyanide (TosMIC).

An iron-mediated highly selective C-H sulfonylmethylation of aniline derivatives with p-toluenesulfonylmethyl isocyanide in a mixture solvent of H2O and PEG400 under an Ar atmosphere has been realized. This transformation proceeds with operational convenience, use of earth-abundant metal catalyst and nontoxic media, broad substrate scope, and good functional group tolerance. The current methodology could be applied to the regioselective C-H sulfonylmethylation of indolines, tetrahydroquinolines, and tertiary anilines.

Correction: Diastereoselective synthesis of chiral 3-substituted isoindolinones via rhodium(III)-catalyzed oxidative C-H olefination/annulation.

Correction for 'Diastereoselective synthesis of chiral 3-substituted isoindolinones via rhodium(iii)-catalyzed oxidative C-H olefination/annulation' by Xue-Hong Li et al., Org. Biomol. Chem., 2021, DOI: 10.1039/d1ob00656h.

Diastereoselective synthesis of chiral 3-substituted isoindolinones via rhodium(III)-catalyzed oxidative C-H olefination/annulation.

A new method for the direct and stereoselective synthesis of 3-substituted isoindolinones via Rh(iii)-catalyzed chiral N-sulfinyl amide directed asymmetric [4 + 1] annulation of benzamides with acrylic esters has been developed. The reaction proceeded through an oxidative C-H olefination and a subsequent cyclization by intramolecular aza-Michael addition, producing a series of diastereoisomeric chiral isoindolinones (20 examples) in generally good yields with a dr value up to 5.5 : 1. The absolute configurations of the newly formed C-stereocenters in the major and minor diastereomers of the catalysis product have been determined by X-ray crystal diffraction analysis to be S and R, respectively. The separation of the major diastereoisomers from the catalysis products and subsequent removal of the N-sulfinyl chiral auxiliary afforded enantiomerically pure (S)-isoindolinones. The application of the obtained (S)-isoindolinones in the synthesis of several biologically active isoindolinones such as (S)-PD172938, (S)-pazinaclone and (S)-pagoclone is presented.

Synthesis of Chiral Bis(3-indolyl)methanes Bearing a Trifluoromethylated All-Carbon Quaternary Stereocenter via Nickel-Catalyzed Asymmetric Friedel-Crafts Alkylation Reaction.

Bis(3-indolyl)methanes are well-known natural products with a broad range of important biological functions including cancer cell growth inhibition and antimicrobial activity. Incorporation of a trifluoromethyl group is known to have a profound effect on the parent compound's biological activities. Here, an efficient method for the synthesis of chiral trifluoromethylated bis(3-indolyl)methanes via a catalytic asymmetric Friedel-Crafts (F-C) alkylation reaction has been established. Both enantiomers of the catalysis products can be obtained by tuning the chiral substituents of the catalyst. With 5 mol % of the Ni(II)/(imidazoline-oxazoline) complex as the catalyst, the F-C reaction of indoles with ß-CF3-ß-(3-indolyl)nitroalkenes proceeded well to afford a series of chiral bis(3-indolyl)methanes bearing a trifluoromethylated all-carbon quaternary stereocenter in generally good yields with excellent enantioselectivities (up to 98% yield and 94% ee). Furthermore, by interchanging the indole moieties of the two reactants, indole vs ß-CF3-ß-(3-indolyl)nitroalkene in the F-C reaction, both enantiomers of a given trifluoromethylated bis(3-indolyl)methane were obtained with high enantioselectivities (89-94% ee) upon removal of the indole N-protecting group in the F-C products. The current work represents the first general catalytic enantioselective approach to the important class of trifluoromethylated bis(3-indolyl)methanes.

Development of a Traceless Directing Group: Cp*-Free Cobalt-Catalyzed C-H Activation/Annulations to Access Isoquinolinones.

A new traceless directing group, 2-(hydroxymethyl)pyridine, has been reported for the Cp*-free cobalt-catalyzed C-H activation/annulation reaction to synthesize isoquinolinones. The reaction exhibits good functional group tolerance, affording products in good to excellent isolated yields under mild conditions. Notably, the directing group can be removed directly in situ along the catalytic process.

Ruthenium-Catalyzed C(sp2)-H Bond Bisallylation with Imidazopyridines as Directing Groups.

A Ru(II)-catalyzed bisallylation of imidazopyridines with vinylcyclopropanes or vinyl cyclic carbonate has been successfully realized. Notably, pharmacophore imidazopyridine was utilized as an intrinsic directing group, which gave access to value-added bisallylated products in high yields via double tandem C-H and C-C/C-O activation. The current methodology was featured with broad substrate scope, good functional group compatibility, and operational simplicity.

Temperature-Controlled Chalcogenation and Chalcogenocyanation of Imidazopyridines in Water under Transition Metal-Free Conditions.

A sustainable and transition metal-free approach for C3 chalcogenation and chalcogenocyanation of imidazopyridines with KXCN (X = S or Se) has been developed under mild conditions. Importantly, this reaction was performed in the presence of catalytic iodine in aqueous medium, which afforded either chalcogenated or chalcogenocyanated imidazopyridines under temperature control. The current protocol featured a broad substrate scope, transition metal-free and organic solvent-free conditions, operational convenience, and gram-scale production.

Synthesis of 7-Amido Indolines by Cp*Co(III)-Catalyzed C-H Bond Amidation.

An efficient Cp*Co(III)-catalyzed C-H bond amidation of indolines at the C7-position using dioxazolone as amidating reagents was first reported. N-Methyl-N-(pyrimidin-2-yl)aniline was also found to be a competent coupling partner. This protocol exhibits several unique characteristics, including excellent isolated yields, good functional group tolerance, and operational convenience. Derivatization reactions revealed this method has great potential for applications in synthesis.

Rh(III)-Catalyzed C-H Cyanation of 2H-Indazole with N-Cyano-N-phenyl-p-toluenesulfonamide.

A Rh(III)-catalyzed direct cyanation of 2H-indazoles with N-cyano-N-phenyl-p-toluenesulfonamide has been realized via a chelation-assisted strategy. The methodology enables regioselective access to various ortho-cyanated phenylindazoles in good yields with a broad substrate scope and good functional group compatibility. The obtained cyanated indazoles could further be converted into other value-added chemicals. Importantly, the current protocol is featured with several characteristics, including a novel cyanating agent, good regioselectivity, and operational convenience.

Cu-Catalyzed Direct C7 Sulfonylation of Indolines with Arylsulfonyl Chlorides.

An efficient Cu-catalyzed direct sulfonylation of indolines with easily accessible sulfonyl chlorides has been realized under an air atmosphere via a chelation-assisted strategy. This protocol exhibits several unique characteristics, including broad substrate scope, good functional group tolerance, and operational convenience, which enable a regioselective access to a variety of C-7 functionalized indoline scaffolds in moderate to good yields. The mechanistic study reveals that the sulfonyl radical might be involved in this transformation.

Asymmetric Michael Addition of 2-Acetyl Azaarenes to ß-CF3-ß-(3-indolyl)nitroalkenes Catalyzed by a Cobalt(II)/(imidazoline-oxazoline) Complex.

The first enantioselective Michael addition of 2-acetyl azaarenes to ß-CF3-ß-(3-indolyl)nitroalkenes has been successfully achieved in the presence of a Co(II)/(imidazoline-oxazoline) complex as the catalyst. The reaction affords a series of CF3- and 3-indole-containing adducts featuring a trifluoromethylated all-carbon quaternary stereocenter in good to excellent yields (up to 99%) and enantioselectivities (up to 96% ee). Furthermore, the functional groups in the adducts including C═O, NO2, and the azaarene provide a large variety of useful transformations, leading to the formation of valuable intermediates such as optically active secondary alcohol, pyrroline, ester, and pyrrolidinone which all contain a 3-substituted indole and a trifluoromethylated all-carbon quaternary stereocenter.

Copper-Catalyzed Double Thiolation To Access Sulfur-Bridged Imidazopyridines with Isothiocyanate.

A copper(I)-catalyzed sulfur-bridged dimerization of imidazopyridines has been developed using isothiocyanate as the sulfur source. This method enables a switchable synthesis of bis(imidazo[1,2- a]pyridin-3-yl)sulfanes or bis(2-(imidazo[1,2- a]pyridin-2-yl)phenyl)sulfanes in the presence of 4-dimethylaminopyridine (DMAP) or K2CO3 when different imidazopyridines were employed. Under optimized conditions, a variety of sulfur-bridged imidazopyridines were obtained in good yields. Moreover, thiourea was proved to be the key intermediate under catalytic system A.

Ditopic Chiral Pineno-Fused 2,2':6',2″-Terpyridine: Synthesis, Self-Assembly, and Optical Properties.

The syntheses of 4'-substituted chiral 2,2':6',2″-terpyridine (tpy) ligands with predetermined configurations and directionalities are rather limited in the supramolecular chemistry field. In this study, a carbazole-linked ditopic chiral ligand L was synthesized using 4'-bromo-substituted pineno-fused tpy 5 as the precursor. Upon complexation with Cd(NO3)2·4H2O and Zn(NO3)2·6H2O, two enantiomerically pure metallosupramolecules, [Cd3L3] and [Zn4L4], have been self-assembled and characterized by NMR, electrospray ionization-mass spectrometry, traveling wave ion mobility-mass spectrometry, and DOSY analysis. In addition, their optical properties are characterized by UV-vis, fluorescence, circular dichroism, and circularly polarized luminescence, suggesting an efficiency transmission and amplification of chirality from the ligand to metal center via self-assembly.

Nickel(ii)-catalyzed C(sp2)-H sulfuration/annulation with elemental sulfur: selective access to benzoisothiazolones.

The first nickel(ii)-catalyzed direct sulfuration/annulation of C(sp2)-H bonds with elemental sulfur has been achieved by using 2-amino alkylbenzimidazole (MBIP-amine) as a N,N-bidentate directing group. This strategy tolerates a wide range of functional groups, furnishing structurally diverse benzoisothiazolone derivatives with benzimidazole skeletons in moderate to excellent yields in a simple and efficient way.