Bridging Plastic Recycling and Organic Catalysis: Photocatalytic Deconstruction of Polystyrene via a C-H Oxidation Pathway.

Chemical recycling of synthetic polymers represents a promising strategy to deconstruct plastic waste and make valuable products. Inspired by small-molecule C-H bond activation, a visible-light-driven reaction is developed to deconstruct polystyrene (PS) into ∼40% benzoic acid as well as ∼20% other monomeric aromatic products at 50 °C and ambient pressure. The practicality of this strategy is demonstrated by deconstruction of real-world PS foam on a gram scale. The reaction is proposed to proceed via a C-H bond oxidation pathway, which is supported by theoretical calculations and experimental results. Fluorescence quenching experiments also support efficient electron transfer between the photocatalyst and the polymer substrate, providing further evidence for the proposed mechanism. This study introduces concepts from small-molecule catalysis to polymer deconstruction and provides a promising method to tackle the global crisis of plastic pollution.

An Integrated Carbon Nitride-Nickel Photocatalyst for the Amination of Aryl Halides Using Sodium Azide.

The synthesis of primary anilines via sustainable methods remains a challenge in organic synthesis. We report a photocatalytic protocol for the selective synthesis of primary anilines via cross-coupling of a wide range of aryl/heteroaryl halides with sodium azide using a photocatalyst powder consisting of nickel(II) deposited on mesoporous carbon nitride (Ni-mpg-CNx ). This heterogeneous photocatalyst contains a high surface area with a visible light-absorbing and adaptive "built-in" solid-state ligand for the integrated catalytic Ni site. The method displays a high functional group tolerance, requires mild reaction conditions, and benefits from easy recovery and reuse of the photocatalyst powder. Thereby, it overcomes the need of complex ligand scaffolds required in homogeneous catalysis, precious metals and elevated temperatures/pressures in existing protocols of primary anilines synthesis. The reported heterogeneous Ni-mpg-CNx holds potential for applications in the academic and industrial synthesis of anilines and exploration of other photocatalytic transformations.

Photocatalytic C-H Azolation of Arenes Using Heterogeneous Carbon Nitride in Batch and Flow.

The functionalization of aryl C(sp2 )-H bonds is a useful strategy for the late-stage modification of biologically active molecules, especially for the regioselective introduction of azole heterocycles to prepare medicinally-relevant compounds. Herein, we describe a practical photocatalytic transformation using a mesoporous carbon nitride (mpg-CNx ) photocatalyst, which enables the efficient azolation of various arenes through direct oxidation. The method exhibits a broad substrate scope and is amenable to the late-stage functionalization of several pharmaceuticals. Due to the heterogeneous nature and high photocatalytic stability of mpg-CNx , the catalyst can be easily recovered and reused leading to greener and more sustainable routes, using either batch or flow processing, to prepare these important compounds of interest in pharmaceutical and agrochemical research.

Visible-Light Promoted C-O Bond Formation with an Integrated Carbon Nitride-Nickel Heterogeneous Photocatalyst.

Ni-deposited mesoporous graphitic carbon nitride (Ni-mpg-CNx ) is introduced as an inexpensive, robust, easily synthesizable and recyclable material that functions as an integrated dual photocatalytic system. This material overcomes the need of expensive photosensitizers, organic ligands and additives as well as limitations of catalyst deactivation in the existing photo/Ni dual catalytic cross-coupling reactions. The dual catalytic Ni-mpg-CNx is demonstrated for C-O coupling between aryl halides and aliphatic alcohols under mild condition. The reaction affords the ether product in good-to-excellent yields (60-92 %) with broad substrate scope, including heteroaryl and aryl halides bearing electron-withdrawing, -donating and neutral groups. The heterogeneous Ni-mpg-CNx can be easily recovered from the reaction mixture and reused over multiple cycles without loss of activity. The findings highlight exciting opportunities for dual catalysis promoted by a fully heterogeneous system.

Visible-Light Promoted C-O Bond Formation with an Integrated Carbon Nitride-Nickel Heterogeneous Photocatalyst.

Ni-deposited mesoporous graphitic carbon nitride (Ni-mpg-CNx) is introduced as an inexpensive, robust, easily synthesizable and recyclable material that functions as an integrated dual photocatalytic system. This material overcomes the need of expensive photosensitizers, organic ligands and additives as well as limitations of catalyst deactivation in the existing photo/Ni dual catalytic cross-coupling reactions. The dual catalytic Ni-mpg-CNx is demonstrated for C-O coupling between aryl halides and aliphatic alcohols under mild condition. The reaction affords the ether product in good-to-excellent yields (60-92 %) with broad substrate scope, including heteroaryl and aryl halides bearing electron-withdrawing, -donating and neutral groups. The heterogeneous Ni-mpg-CNx can be easily recovered from the reaction mixture and reused over multiple cycles without loss of activity. The findings highlight exciting opportunities for dual catalysis promoted by a fully heterogeneous system.

Visible-Light Flow Reactor Packed with Porous Carbon Nitride for Aerobic Substrate Oxidations.

A triphasic photocatalytic reactor employing a mesoporous carbon nitride photocatalyst and aerobic O2 was assembled to operate under continuous flow conditions. This reactor design allows for facile downstream processing and reusability in multiple flow cycles. The selective aerobic oxidation of alcohols and amines was chosen to demonstrate the applicability and performance advantage of this flow approach compared to that of conventional batch photochemistry. This precious-metal-free photocatalytic flow system operates under benign reaction conditions (visible light, low pressure, and mild temperature) and will stimulate the exploration of other oxidative reactions in a sustainable, scalable, and affordable manner.

Palladium-Catalyzed Chemoselective Activation of sp3 vs sp2 C-H Bonds: Oxidative Coupling To Form Quaternary Centers.

The oxidative activation of alkyl C-H bonds vs arene C-H bonds with Pd(OAc)2 has been found to be generalizable to a number of nucleophilic substrates allowing the formation of a range of hindered quaternary centers. The substrates share a common mechanistic path wherein Pd(II) initiates an oxidative dimerization. The resultant dimer modifies the palladium catalyst to favor activation of alkyl C-H bonds in contrast to the trends typically observed via a concerted metalation deprotonation mechanism. Notably, insertion occurs at the terminus of the alkyl arene for hindered substrates. Two different oxidant systems were discovered that turn over the process. Parameters have been identified that predict, which substrates are productive in this reaction.

Carbon nitride as a heterogeneous visible-light photocatalyst for the Minisci reaction and coupling to H2 production.

Cyanamide functionalised carbon nitride powder is reported as a photocatalyst for direct Minisci-type coupling of heteroarenes with ethers, alcohols, and amides using atmospheric oxygen as the oxidant at room temperature. This mild protocol displays broad substrate scope, good functional group tolerance and the catalyst can be easily isolated and reused for several cycles. It thereby addresses the two major limitations of previously reported photoredox-mediated Minisci reactions: (i) use of expensive and potentially harmful non-recyclable photocatalysts, and (ii) requirement of a stoichiometric amount of strong chemical oxidant. Finally, using platinum as a co-catalyst with the carbon nitride allows this light-mediated reaction to generate two value-added products under an anaerobic atmosphere - functionalised heteroarenes and H2 fuel.

Cobalt-Catalyzed Cyclization of N-Methoxy Benzamides with Alkynes using an Internal Oxidant through C-H/N-O Bond Activation.

The cyclization of substituted N-methoxy benzamides with alkynes in the presence of an easily affordable cobalt complex and NaOAc provides isoquinolone derivatives in good to excellent yields. The cyclization reaction is compatible with a range of functional group-substituted benzamides, as well as ester- and alcohol-substituted alkynes. The cobalt complex [Co(III) Cp*(OR)2 ] (R=Me or Ac) serves as an efficient catalyst for the cyclization reaction. Later, isoquinolone derivatives were converted into 1-chloro and 1-bromo substituted isoquinoline derivatives in excellent yields in the presence of POCl3 or PBr3 .

Ruthenium- and palladium-catalyzed consecutive coupling and cyclization of aromatic sulfoximines with phenylboronic acids: an efficient route to dibenzothiazines.

A ruthenium-catalyzed ortho arylation of aromatic sulfoximines with aromatic boronic acids followed by intramolecular cyclization in the presence of a palladium catalyst, providing dibenzothiazine derivatives in two consecutive steps, is described.

A 1,3-amino group migration route to form acrylamidines.

A novel 1,3-amino group migration strategy for the synthesis of acrylamidines is presented. Cu(i) catalyzed reaction of N,N-disubstituted propargylamine with tosylazide generates a highly reactive ketenimine intermediate which is trapped by a tethered amino group leading to the rearrangement reaction.