Unleashing the photocatalytic potential of a noble-metal-free heteroleptic copper complex-based nanomaterial for an enhanced aza-Henry reaction.

In this work, we fabricated a versatile and noble metal free copper-based heterogeneous photocatalyst, representing a green shift away from precious group metals such as Ir, Ru, Pt, which have been widely utilized as photocatalysts. The successfully synthesized and characterized copper photocatalyst was employed to establish a cross dehydrogenative coupling via C-H activation between tertiary amines and carbon nucleophiles. The highly efficient copper-based photocatalyst was characterized by numerous physico-chemical techniques, which confirmed its successful formation as well as its high activity. Inductively coupled plasma (ICP-OES) analysis revealed that the composite Cu@Xantphos@ASMNPs had a very high loading of 0.423 mmol g-1 of copper. The magnetic Cu@Xantphos@ASMNPs were utilized as a potential heterogeneous photocatalyst for the very facile and regioselective conversion of aryl tetrahydroqinoline to the respective nitroalkyl aryl tetrahydroisoquinoline in high yield using air as an oxidant and methanol as a green solvent with irradiation with visible light under mild reaction conditions. Additionally, the catalyst shows exceptional chemical stability and reusability without any agglomeration even after several cycles of use, which is one of the key features of this material, rendering it a potential candidate from economic and environmental perspectives.

Development of heterogeneous photocatalysts via the covalent grafting of metal complexes on various solid supports.

To date, remarkable progress has been achieved in the development of photocatalysts owing to their high activity, selectivity, and tunable light absorption in the visible light range. Recently, heterogeneous photocatalytic systems have emerged as potential candidates due to their beneficial attributes (e.g., high surface area, ease of functionalization and facile separation). Herein, we provide a concise overview of the rational design of heterogeneous photocatalysts by grafting photoactive complexes on heterogeneous support matrices via covalent grafting and their detailed characterization techniques, which have been followed by the landmark examples of their applications. Also, major challenges and opportunities in the forthcoming progress of these appealing areas are emphasised.

Expedient Access to Polyaromatic Biaryls by Unconventional Ag-Catalyzed Cycloaromatization of Alkynylthiophenes and Au-Catalyzed Double C-H Activation.

An unconventional approach for the regioselective synthesis of polyaromatic biaryls via site-selective Ag-catalyzed twofold electrophilic cycloisomerization followed by Au-catalyzed double C-H activation is described. The developed process allows the synthesis of highly decorated biaryls with excellent regioselectivity. As revealed by DFT computations, the reaction represents a rare example of C1-C5 endo-exo and C1-C6 endo-endo cycloaromatization. The formation of the 6-membered ring is predicted to be the fruit of an uncommon SEAr on a vinyl carbocation.

Tandem 6π-Azatriene Electrocyclization of Fused Amino-cyclopentenones: Synthesis of Functionalized Pyrrolo- and Indolo-quinoxalines.

A tandem 6π-azacyclization approach for the synthesis of diversified pyrrolo/indolo[1,2-a]quinoxalines from amino-cyclopentenones has been developed. The reaction proceeds through a trifluoroacetic-acid-mediated 6π-electrocyclization and concomitant opening of the cyclopentenone ring. The advantageous features of the developed chemistry include transition-metal-free conditions, operational simplicity, and a broad substrate scope. Further X-ray crystallographic studies confirm the assigned structures of the fused heterocycles.

Synthesis of cyclopentaquinolinone and cyclopentapyridinone from ortho-alkynyl-N-arylaldehyde via superbase-promoted C-N, C-O and C-C bond formation.

An environmentally benign, transition metal-free, superbase-mediated intramolecular annulation of o-alkynylaldehydes with primary amines forms highly functionalized amino-substituted cyclopentaquinolinones and cyclopentapyridinones via C-N, C-C, and C[double bond, length as m-dash]O bond formation. Contrary to the traditional approaches of ring closures, a different mode of annulation is disclosed. The protocol involves the in situ generations of imine intermediate followed by potassium hydroxide-promoted intramolecular cyclization and subsequent dimethyl sulfoxide induced dehydrogenation leads to the formation of N-heterocycles. X-ray crystallographic studies support the assigned structures of the amino-fused N-heterocycles.

On water: iodine-mediated direct construction of 1,3-benzothiazines from ortho-alkynylanilines by regioselective 6-exo-dig cyclization.

Herein, we report the 6-exo-dig ring closure of ortho-alkynylanilines with readily available aroyl isothiocyanate. An environmentally benign, metal- and base-free, iodine promoted cascade synthesis of highly functionalized (benzo[1,3]thiazin-2-yl)benzimidic acids has been accomplished via in situ generated ortho-alkynylthiourea. The established methodology employs the abundant chemical feedstock of ortho-alkynylanilines and aroyl isothiocyanates and could be applied in the late-stage synthesis of pharmaceutically active 1,3-benzothiazine containing molecules. Furthermore, the discovered protocol exclusively delivers bis (benzo[1,3]thiazin-2-yl)dibenzimidic acid products and preserves the iodo-olefin substitution pattern which can be exploited by further derivatization.

On Water: Metal-Free Synthesis of Highly Functionalized Benzothiazolylidene from ortho-Haloanilines.

An environmentally benign, transition-metal-free organic base promoted one-pot cascade synthesis of highly functionalized benzo[ d]thiazol-2(3 H)-ylidene benzamide in the presence of water was accomplished by three-component reaction of ortho-iodoanilines, acrylates, and aroyl isothiocyanates. The protocol involves the in situ generation of thiourea intermediate followed by triethylamine induced intramolecular SNAr displacement reaction and subsequent Michael addition onto acrylate leads to the formation of benzo[ d]thiazol-2(3 H)-ylidene benzamide. Benzo[ b]thiazole is also generated in good yields using amidation and intramolecular aromatic nucleophilic substitution chemistry. The control experiments support the proposed mechanistic pathway. Further X-ray crystallographic studies confirmed the assigned structures of the fused benzamide.

Pd-Catalyzed one-pot sequential cross-coupling reactions of tetrabromothiophene.

Unsymmetrical one-pot sequential cross-coupling reactions of sterically hindered tetrabromothiophene with arylboronic acid and an alkyne/alkene to afford selective bi-, tri-, and tetrasubstituted aryl/alkynyl-thiophenes with the aid of a palladium catalyst were described. The reaction proceeds via a site-selective Suzuki/Sonogashira coupling, followed by selective Sonogashira, Suzuki and Heck coupling reactions. This methodology has demonstrated an important framework for the synthesis of organic scaffolds.

Ag(i)-Catalyzed cycloisomerization reactions: synthesis of substituted phenanthrenes and naphthothiophenes.

This paper describes silver catalyzed synthesis of substituted phenanthrenes and naphthothiophenes from ortho-alkylated biaryl derivatives via 6-endo-dig intramolecular alkyne-arene coupling. The mechanistic study reveals that 6-endo-dig cyclization proceeds through initial π-coordination of the alkyne unit followed by a Friedel-Crafts-type electrophilic aromatic cyclization at the adjacent arene ring. X-ray crystallographic studies further supported the formation of carbocycles.