Cobalt-Catalyzed Regioselective C8-H Sulfoxamination of 1-Naphthylamine Derivatives with NH-Sulfoximines.

A simple cobalt-catalyzed, picolinamide-directed C8-H sulfoxamination of 1-naphthalamides with NH-sulfoximines has been developed. This cross-dehydrogenative C-H/N-H coupling reaction offers a facile route to N-arylated sulfoximines, exhibiting high yields, a broad substrate scope, and excellent functional group tolerance and scalability.

3D Porous Polymer Scaffold-Conjugated KGF-Mimetic Peptide Promotes Functional Skin Regeneration in Chronic Diabetic Wounds.

The re-epithelialization process gets severely dysregulated in chronic nonhealing diabetic foot ulcers/wounds. Keratinocyte growth factor (KGF or FGF-7) is the major modulator of the re-epithelialization process, which regulates the physiological phenotypes of cutaneous keratinocytes. The existing therapeutic strategies of growth factor administration have several limitations.

Synthesis of Tetrazolo[5,1-]isoquinolines via a Suzuki-Miyaura Coupling Reaction/[3 + 2] Cycloaddition Sequence.

An efficient copper-catalyzed method for the synthesis of tetrazolo[5,1-]isoquinolines has been developed starting from alkenyl-1,2-bis(boronates). The domino reaction underwent a Suzuki-Miyaura cross-coupling reaction and an azidation followed by an in situ [3 + 2] cycloaddition. Regioselective synthesis has been demonstrated by inverting the Suzuki-Miyaura cross-coupling reaction and the azidation.

Palladium-Catalyzed Chelation-Assisted Aldehyde C-H Bond Activation of Quinoline-8-carbaldehydes: Synthesis of Amides from Aldehydes with Anilines and Other Amines.

A palladium-catalyzed chelation-assisted direct aldehyde C-H bond amidation of quinoline-8-carbaldehydes with an amine was developed under mild reaction conditions. A wide range of amides were obtained in good to excellent yields from aldehyde with a variety of aniline derivatives and aliphatic amines. Our methodology was successfully applied to synthesize known DNA intercalating agents and can be easily scaled up to a gram scale.

Regio- and stereocontrolled synthesis of borylated -enynes, -enediynes and derivatives from alkenyl-1,2-bis-(boronates).

An efficient stereo-controlled synthesis of enyne and enediyne derivatives, sequential Suzuki-Miyaura coupling reactions from easily prepared 1-alkene-1,2-diboronic esters and alkynyl bromides, is reported. The resulting enyne boronic esters were subjected to Borono-Mannich and Suzuki coupling reactions independently to obtain α,β-unsaturated aminoester and tri-substituted olefin derivatives, respectively. Additionally, divergent syntheses of triazole and cyclopropylboronate derivatives are also reported.

Synthesis of Fused Tetracyclic Compounds via Oxidative Annulation: Access to Copper-Catalyzed Indolo[1,2-]quinolines and to Ruthenium-Catalyzed Isoquinolin-1[2]-ones.

A facile double oxidative annulation of (en-3-yn-1-yl)phenylbenzamides was developed allowing us to synthetize fused tetracyclic compounds. Under copper catalysis, the reaction proceeds with high efficiency and leads to new indolo[1,2-]quinolines via a decarbonylative double oxidative annulation. On the other hand, under ruthenium catalysis, new isoquinolin-1[2]-ones were obtained via a double oxidative annulation.

Palladium-Catalyzed Directed Aldehyde C-H Arylation of Quinoline-8-carbaldehydes: Exploring the Reactivity Differences between Aryl (Pseudo) Halides.

We have developed a method for Pd-catalyzed direct C-H arylation of quinoline-8-carbaldehydes with either aryl iodides or aryl diazonium salts for the synthesis of aryl quinolinyl ketones. Aryl iodide substituted with an electron-donating group favors the reaction, whereas aryl diazonium salt substituted with an electron-withdrawing group showed excellent reactivity. A range of aryl quinolinyl ketones were synthesized in good-to-excellent yields, with very good functional group tolerance.

pH-controlled regioselective nucleophilic ring-opening of epoxide: an improved process for the preparation of ()-(-)- or ()-(+)-3-hydroxytetrahydrofuran.

An environmentally benign, cost-effective and scalable process for the preparation of both the enantiomers of 3-hydroxytetrahydrofuran has been developed. pH-Controlled ring opening of enantiomerically pure epichlorohydrins with cyanohydrin is the key step of the process. The entire protocol does not require any column purification.

Simmons-Smith Cyclopropanation of Alkenyl 1,2-Bis(boronates): Stereoselective Access to Functionalized Cyclopropyl Derivatives.

A Simmons-Smith stereodefined procedure for the synthesis of cyclopropyl-1,2-bis(boronates) has been developed starting from the corresponding alkenes. The resulting compounds were then subjected to regioselective Suzuki-Miyaura couplings to produce diversely tri- or tetra-substituted arylcyclopropanes in good yields. Further functionalization with 2-lithiothiophene provided 1,2-bis(aryl)cyclopropanes.

Total synthesis of remdesivir.

Remdesivir, the first drug approved by the FDA to treat COVID-19, is in high demand for patients infected with the SARS-CoV-2 virus. Herein, we report a facile approach minimizing the protecting group manipulations to afford remdesivir in good overall yield.

Copper(II) mediated C-H alkoxylation of aromatic amines using organic peroxides: efficient synthesis of hindered ethers.

Synthesis of hindered alkyl aryl ether derivatives (R-O-Ar) remains a huge challenge and highly desirable in organic and medicinal chemistry because extensive substitution on the ether bond prevents the undesired metabolic process and thus avoids rapid degradation . Herein, we report an unprecedented hindered alkoxylation of picolinamide attached aromatic amines using economic copper salt and organic peroxide to get highly desirable α-tertiary alkyl aryl ethers.

C-H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions.

An atom-economical and efficient route for the direct amidation and amination of aryl C-H bonds using our synthesized recyclable heterogeneous Cu-MnO catalyst is reported here. The direct C-H amidation was carried out using a simple amide without any preactivated coupling partner, and simple air was used as the sole oxidant. The reaction proceeds very smoothly with a broad range of substrates containing numerous functional groups in very good to excellent yields.

Copper-Mediated Synthesis of ()-1-Azido and ()-1,2-Diazido Alkenes from 1-Alkene-1,2-diboronic Esters: An Approach to Mono- and 1,2-Di-(1,2,3-Triazolyl)-Alkenes and Fused Bis-(1,2,3-Triazolo)-Pyrazines.

A stereoselective and convenient route has been demonstrated to access ()-1,2-diazido alkenes from the corresponding 1,2-diboronic esters a copper-mediated reaction with sodium azide. Alternately, mono-functionalization was regioselectively carried out with trimethylsilyl azide as an azidation reactant. The conversion of bis-azides to the corresponding bis-triazoles can be readily achieved in the presence of copper sulfate and sodium ascorbate, while the modification of the catalytic system opened a new convenient route to bis-triazolo-pyrazines, a new class of fused heterocycles.

Room-Temperature Synthesis of Isoindolone Spirosuccinimides: Merger of Visible-Light Photocatalysis and Cobalt-Catalyzed C-H Activation.

A room-temperature C-H bond functionalization of benzamides has been developed by merging a photocatalyst with a cobalt catalyst for the synthesis of isoindolone spirosuccinimides. The reaction proceeds in aerobic conditions and does not require any sacrificial external oxidants such as Ag(I) or Mn(III) salts. Visible light activates the photocatalyst, and it acts as an electron-transfer reagent and helps in the fundamental organometallic steps by modulating the oxidation state of the cobalt complex.

Micro-electro-flow reactor (μ-EFR) system for ultra-fast arene synthesis and manufacture of daclatasvir.

The World Health Organization (WHO) has listed daclatasvir (DCV), symmetrical arene, as one of the essential medicines for human health. DCV manufacturing is usually carried out in a non-continuous or "batch" approach over multiple locations and is severely limited by long production times (3-10 days), resulting in non-affordability (highly expensive) and disruption of the potential chain supply. Here, we report the total process system including the development of a novel electro-flow reactor containing patterned electrodeposited Ni or Pt nanoparticles over a copper electrode for a C-C coupling reaction in a co-reductant/oxidant-free, ultra-fast process for symmetrical substituted/unsubstituted biphenyl synthesis.

Total Synthesis of Callyspongiolide: An Anticancer Marine Natural Product.

The stereoselective total synthesis of cytotoxic marine macrolide callyspongiolide has been reported. The 14-membered macrolactone ring along with -olefin in the molecule was constructed via an intramolecular Horner-Wadsworth-Emmons olefination in a -selective fashion. The other -olefinic moiety as well as the C9 stereocenter was introduced via stereoselective addition of the methyl group in an S2' fashion.

N-Doped Yellow TiO Hollow Sphere-Mediated Visible-Light-Driven Efficient Esterification of Alcohol and N-Hydroxyimides to Active Esters.

Herein we report a simple synthetic protocol for N-doped yellow TiO (N-TiO ) hollow spheres as an efficient visible-light-active photocatalyst using aqueous titanium peroxocarbonate complex (TPCC) solution as precursor and NH OH. In the developed strategy, the ammonium ion of TPCC and NH OH acts as nitrogen source and structure-directing agent. The synthesized N-TiO hollow spheres are capable of promoting the synthesis of active esters of N-hydroxyimide and alcohol through simultaneous selective oxidation of alcohol to aldehyde followed by cross-dehydrogenative coupling (CDC) under ambient conditions upon irradiation of visible light.

Visible Light-Promoted Photocatalytic C-5 Carboxylation of 8-Aminoquinoline Amides and Sulfonamides via a Single Electron Transfer Pathway.

An efficient photocatalytic method was developed for the remote C5-H bond carboxylation of 8-aminoquinoline amide and sulfonamide derivatives. This methodology uses in situ generated CBr radical as a carboxylation agent with alcohol and is further extended to a variety of arenes and heteroarenes to synthesize the desired carboxylated product in moderate-to-good yields. The reaction proceeding through a single electron transfer pathway was established by a control experiment, and a butylated hydroxytoluene-trapped aryl radical cation intermediate in high-resolution mass spectrometry was identified.

Visible-light-driven Efficient Photocatalytic Reduction of Organic Azides to Amines over CdS Sheet-rGO Nanocomposite.

CdS sheet-rGO nanocomposite as a heterogeneous photocatalyst enables visible-light-induced photocatalytic reduction of aromatic, heteroaromatic, aliphatic and sulfonyl azides to the corresponding amines using hydrazine hydrate as a reductant. The reaction shows excellent conversion and chemoselectivity towards the formation of the amine without self-photoactivated azo compounds. In the adopted strategy, CdS not only accelerates the formation of nitrene through photoactivation of azide but also enhances the decomposition of azide to a certain extent, which entirely suppressed formation of the azo compound.

Hydrogenated MoS QD-TiO heterojunction mediated efficient solar hydrogen production.

Herein, we report the development of a hydrogenated MoS QD-TiO (HMT) heterojunction as an efficient photocatalytic system via a one-pot hydrothermal reaction followed by hydrogenation. This synthetic strategy facilitates the formation of MoS QDs with an enhanced band gap and a proper heterojunction between them and TiO, which accelerates charge transfer process. Hydrogenation leads to oxygen vacancies in TiO, enhancing the visible light absorption capacity through narrowing its band gap, and sulfur vacancies in MoS, which enhance the active sites for hydrogen adsorption.

Visible-Light-Induced Efficient Selective Oxidation of Nonactivated Alcohols over {001}-Faceted TiO with Molecular Oxygen.

In the presence of molecular oxygen, a {001}-faceted nanocrystalline anatase TiO catalyst enabled the selective oxidation of nonactivated aliphatic alcohols to the corresponding aldehydes or ketones under visible light. The reaction shows excellent conversion and selectivity towards the formation of the carbonyl products without over-oxidation to the corresponding carboxylic acids. The exceptional reactivity of the catalyst is possibly due to the absorption of visible light originating from a stronger interaction of alcohol with the {001} facet, which facilitates the modification of the band structure of TiO , thus facilitating the photogenerated hole transfer and subsequent oxidation processes.

Total Synthesis of the Proposed Structure of Maltepolide C.

The first total synthesis of the proposed structure of cytotoxic macrolide maltepolide C has been achieved via an E-selective intramolecular Heck cyclization as a key step. Other key features of the synthesis are Z-selective Wittig olefination, Sharpless asymmetric dihydroxylation followed by Williamson-type cyclo-etherification, Brown asymmetric allylation, and Noyori reduction of an alkynone. Detailed NMR study confirms the structure and stereochemistry of the synthetic maltepolide C unambiguously.

Synthetic studies of callyspongiolide: synthesis of the macrolactone core of the molecule.

A concise synthetic strategy has been developed for the synthesis of the macrolactone core 2 of a unique polyketide callyspongiolide 1. The key features of the strategy included an Evan's asymmetric alkylation, diastereoselective Michael type alkylation, Brown's asymmetric allylation reaction, an allylic alkylation of an activated Z-allylic alcohol and an intramolecular Z-selective intramolecular H-W-E olefination.

Efficient photocatalytic selective nitro-reduction and C-H bond oxidation over ultrathin sheet mediated CdS flowers.

We report here a visible light driven selective nitro-reduction and oxidation of saturated sp(3) C-H bonds using ultrathin (0.8 nm) sheet mediated uniform CdS flowers as catalyst under a household 40 W CFL lamp and molecular oxygen as oxidant. The CdS flowers were synthesized using a simple surfactant assisted hydrothermal method.

Synthesis of fully functionalized aglycone of lycoperdinoside A and B.

This article reported the synthesis of fully functionalized aglycone of lycoperdinoside A and B. Pd-catalyzed Stille-Migita cross coupling between E-vinyl iodide 6 and E-vinyl stannane 23 established the highly substituted E,E-diene unit present in lycoperdinoside A and B. The other two Z-olefins present in the molecule were introduced by means of cis-selective Horner-Wadsworth-Emmons reaction with Still-Gennari phosphonate.