Efficient Adsorptive Removal of Methylene Blue Dye from Aqueous Solution Using Eragrostis Teff Biomass-Derived Nitrogen and Phosphorus-Codoped Carbon Quantum Dots.

Carbon quantum dots have a great application potential in environmental protection via adsorption technology due to their large specific surface area and negative zeta potential. In this work, nitrogen and phosphorus-codoped carbon quantum dots (NP-CQDs) with a large specific surface area and negative zeta potential were successfully synthesized by a single-step hydrothermal synthesis. Batch adsorption studies were utilized to assess the adsorbent's capacity to remove common methylene blue (MB) dye contaminants from an aqueous solution. The experiment showed that MB dye could be removed in 30 min under optimum experimental conditions, with a removal efficiency of 93.73%. The adsorbent's large surface area of 526.063 m2/g and negative zeta potential of -12.3 mV contribute to the high removal efficiency. The Freundlich isotherm model fits the adsorption process well at 298 K, with R2 and n values of 0.99678 and 4.564, respectively, indicating its applicability. A kinetic study demonstrated that the pseudo-second-order model, rather than the pseudo-first-order model, is more suited to represent the process of MB dye adsorption onto NP-CQDs. This research established a simple and cost-effective method for developing a highly efficient NP-CQD adsorbent for organic dye degradation by adsorption.

A Dual Cobalt-Photoredox Catalytic Approach for Asymmetric Dearomatization of Indoles with Aryl Amides via C-H Activation.

In this study, we unveil a novel method for the asymmetric dearomatization of indoles under cobalt/photoredox catalysis. By strategically activating C-H bonds of amides and subsequent migratory insertion of  p-bonds present in indole as reactive partner, we achieve syn-selective tetrahydro-5H-indolo[2,3-c]isoquinolin-5-one derivatives with excellent yields and enantiomeric excesses of up to >99%. The developed method operates without a metal oxidant, relying solely on oxygen as the oxidant and employing an organic dye as a photocatalyst under irradiation. Control experiments and stoichiometric studies elucidate the reversible nature of the enantiodetermining C-H activation step, albeit not being rate-determining. This study not only expands the horizon of cobalt-catalyzed asymmetric C-H bond functionalization, but also showcases the potential synergy between cobalt and photoredox catalysis in enabling asymmetric synthesis of complex molecules.

Reversal of Regioselectivity in Asymmetric C-H Bond Annulation with Bromoalkynes under Cobalt Catalysis.

Metal-catalyzed asymmetric C-H bond annulation strategy offers a versatile platform, allowing the construction of complex P-chiral molecules through atom- and step-economical fashion. However, regioselective insertion of π-coupling partner between M-C bond with high enantio-induction remain elusive. Using commercially available Co(II) salt and chiral-Salox ligands, we demonstrate an unusual protocol for the regio-reversal, enantioselective C-H bond annulation of phosphinamide with bromoalkyne through desymmetrization. The reaction proceeds through ligand-assisted enantiodetermining cyclocobaltation followed by regioselective insertion of bromoalkyne between Co-C, subsequent reductive elimination, and halogen exchange with carboxylate resulted in P-stereogenic compounds in excellent ee (up to >99 %). The isolation of cobaltacycle involved in the catalytic cycle and the outcome of control experiments provide support for a plausible mechanism.

Allenyl Carbonate as a Butadiene Surrogate in Cobalt-Catalyzed Crotylation of Aldehydes.

Allenyl carbonate was used as a 1,3-butadiene surrogate to develop a photocatalytically sustainable protocol for cobalt-catalyzed crotylation of aldehydes. The developed method tolerated a wide range of aromatic and aliphatic aldehydes with retention of functional groups under mild conditions and produced good-to-excellent yields of crotylated secondary alcohols. Based on preliminary mechanistic studies and literature precedents, a plausible mechanism is proposed.

Cp*CoIII-Catalyzed C(7)-H Bond Annulation of Indolines with Alkynes.

An efficient protocol for the synthesis of biologically essential pyrroloquinolinones has been developed under Cp*CoIII catalysis, which involves a cascade reaction of C(7)-H alkenylation with alkynes followed by nucleophilic addition. A wide variety of internal alkynes including enyne, diyne, and ynamide and more challenging terminal alkynes were successfully employed for the annulation in good to excellent yield with high regioselectivity.

CoIII -Catalyzed Isonitrile Insertion/Acyl Group Migration Between C-H and N-H bonds of Arylamides.

A general efficient and site-selective cobalt-catalyzed insertion of isonitrile into C-H and N-H bonds of arylamides through C-H bond activation and alcohol assisted intramolecular trans-amidation is demonstrated. This straightforward approach overcomes the limitation by the presence of strongly chelating groups. Isolation of CoIII -isonitrile complex B has been achieved for the first time to understand the reaction mechanism.

Isolation of Cp*CoIII -Alkenyl Intermediate in Efficient Cobalt-Catalyzed C-H Alkenylation with Alkynes.

A general and efficient procedure for C-H alkenylation of arenes with a broad substrate scope catalyzed by Cp*CoIII was demonstrated with alkynes. A highly selective mono-alkenylation and sequential bis-C-H bond functionalization was displayed to exemplify the versatility of the cobalt catalyst. Isolation of cationic Cp*CoIII -alkenyl intermediate was achieved under identical catalytic conditions to further establish the proposed pathway.

Cp*CoIII -Catalyzed Bis-isoquinolone Synthesis by C-H Annulation of Arylamide with 1,3-Diyne.

Cp*CoIII -catalyzed highly regioselective mono- and bis-annulation of arylamides with 1,3-diynes using N-OMe as an internal oxidant is demonstrated. This atom-economical transformation does not require any external oxidant and tolerates many functional groups. Various symmetrical and unsymmetrical heterocycles (homo and hetero) are accessed with predictable regio- and chemoselectivity.

Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols.

Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product.

Cp*Co(III) -Catalyzed C(sp(3) )-H Bond Amidation of 8-Methylquinoline.

An efficient and external oxidant-free, Cp*Co(III) -catalyzed C(sp(3) )-H bond amidation of 8-methylquinoline, using oxazolone as an efficient amidating agent, is reported for the first time under mild conditions. The reaction is selective and tolerates a variety of functional groups. Based on previous reports and experimental results, the deprotonation pathway proceeds through an external base-assisted concerted metalation and deprotonation process.

Cobalt(III)-Catalyzed Dehydrative [4+2] Annulation of Oxime with Alkyne by C-H and N-OH Activation.

Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable Cp*Co(III) neutral complex is employed as the catalyst for this redox-neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.

Carboxylate Assisted Ni-Catalyzed C-H Bond Allylation of Benzamides.

A one-step synthetic method was developed for allylation of benzamides using Ni(COD)2/RCO2 H and [Ni(µ-H2O)(OOCCMe3)2 (HOOCCMe3)2]2 (A') catalytic system. Efficient, well-defined, air and moisture-stable Ni-pivalate complex was isolated and employed in catalytic allylation. The influence of solvent on product selectivity was also investigated.

Enantioselective C-H bond functionalization under Co(III)-catalysis.

While progress in enantioselective C-H functionalization has been accomplished by employing 4d and 5d transition metal-based catalysts, the rapid depletion of these metals in the earth's crust poses a serious threat to making these protocols sustainable. On the other hand, because of their unique reactivity, low toxicity, and high earth abundance, newer strategies utilizing affordable 3d transition metals have come to the forefront. Among the first-row transition metals, high-valent cobalt has recently attracted a lot of attention for catalytic C-H functionalization with mono and bidentate directing groups. This approach was extended for asymmetric catalysis due to a fairly thorough knowledge of its catalytic cycles. Four major themes have been investigated as a result of this insight: (1) rational design of a chiral Cp#Co(III)-catalyst, (2) chiral carboxylic acid with achiral Cp*Co(III)-catalysts using monodentate directing groups, (3) cobalt/salox-based systems, and (4) cobalt/chiral phosphoric acid-based hybrid systems with bidentate directing groups. Herein, we highlight the recent developments in high-valent cobalt-catalyzed enantioselective C-H functionalization up to October 2023, with the strong belief that the current state-of-the-art can attract considerable interest in the synthetic community, encouraging discoveries in the evolving landscape of asymmetric catalysis.

Transition metal catalyzed nucleophilic allylic substitution: activation of allylic alcohols via π-allylic species.

Modern organic synthesis now requires efficient atom economical synthetic methods operating under greener pathways to achieve C-C and C-heteroatom bond formation. Direct activation of allylic alcohols in the presence of transition metal catalysts leading to electrophilic π-allyl metal intermediates represents such a promising target in the field of nucleophilic allylation reactions. During the last decade, this topic of recognized importance has become an emerging area, and selected transition metals, sometimes associated with alcohol activators, have brought elegant solutions for performing allylic substitution directly from alcohols in a regio, stereo and enantioselective manner.

A functional-group-tolerant catalytic trans hydrogenation of alkynes.

Against the rules: during the hundred years following Sabatier's groundbreaking work on catalytic hydrogenation, syn delivery of the H atoms to the π system of a substrate remained the governing stereochemical rule. An exception has now be found with the use of cationic [Cp*Ru] templates, which accounts for the first practical, functional-group-tolerant, broadly applicable and highly E-selective semihydrogenation method for alkynes.

Cp*Co(III)-Catalyzed C(8)-Nucleophilic Cascade Cyclization of Quinoline N-Oxide with 1,6-Enyne.

The C(8)-selective nucleophilic cascade cyclization of quinoline N-oxide with easily derived 1,6-enyne from phenol derivatives is demonstrated. A variety of quinoline N-oxide and alkynes are discovered to be suitable for producing a library of quinoline N-oxide tethered cis-hydrobenzofurans with high yields and excellent functional group tolerance. The utility of the protocol has been accomplished by post-synthetic modification of the cyclized product. The mechanistic studies indicate a base-assisted internal electrophilic-type substitution (BIES)-type pathway for C-H bond activation, and electrospray ionization mass spectrometry (ESI-MS) analysis of the stoichiometric reaction confirmed the formation of a key five-membered cobaltacycle.

Hydrogenation and dehydrogenation of N-heterocycles under Cp*Co(III)-catalysis.

To realize the goal of a carbon-free energy economy, it is crucial to discover reactions that utilize sustainable resources as alternatives to fossil feedstocks. In this study, a well-defined, air-stable Cp*Co(III)-catalyst for transfer hydrogenation of quinoline derivatives and oxidative dehydrogenation of cyclic amines in water is developed. While the former reaction is promoted by formic acid as a transfer hydrogenation reagent, the latter is mediated by molecular oxygen as the sole oxidant. These processes provide new avenues for the investigation of air-stable cobalt catalysts for environmentally benign hydrogenation and dehydrogenation reactions.

Isoquinoline derivatives via stepwise regioselective sp(2) and sp(3) C-H bond functionalizations.

Efficient and practically attractive stepwise ruthenium- and palladium-catalyzed regioselective C-H bond functionalizations were achieved to produce 4-substituted tetrahydroisoquinoline derivatives featuring various heteroaromatic substructures in moderate to good yields. Both ruthenium- and palladium-based catalytic processes generated nontoxic and easily separable side products.

Methanol as a hydrogen source: room-temperature highly-selective transfer hydrogenation of α,ß-unsaturated ketones.

The described system offers an ideal, user-friendly protocol for the chemoselective homogeneous hydrogenation of α,ß-unsaturated ketones at room temperature using methanol as a liquid organic hydrogen carrier. Excellent yields were achieved with an in situ-prepared phosphine-free Cp*Ir(III)/bipyridonate complex. Chemoselective reduction with other reducible functionalities and late-stage functionalization were also explored.

Iron-Catalyzed α-Methylation of Ketones Using Methanol as the C1 Source under Photoirradiation.

A mild, environmentally benign approach for α-methylation of ketones utilizing methanol as the C1 source under visible light has been developed. The reaction conditions were favorable for a wide range of ketones with both aromatic and aliphatic backbones, allowing for good-to-excellent yields of the respective products. The tentative mechanism is postulated after preliminary mechanistic and kinetic experiments.