Blue LED-Mediated Syntheses of Arylazo Phosphine Oxides and Phosphonates via N-P Bond Formation.

The synthesis of (E)-diphenyl(aryldiazenyl)phosphine oxides and dialkyl (E)-(aryldiazenyl)phosphonates via visible light-mediated N-P bond formation between diazo species and phosphine oxides and phosphite derivatives, respectively, is described. The diazo species were generated via the reaction of aniline with isoamyl nitrite, which upon reaction with phosphorus surrogates generated arylazophosphine oxides and arylazo phosphonates in good to excellent yields. This sustainable chemical process offers a broad substrate scope and reasonably viable product formation.

Blue LED-Promoted Syntheses of Phosphorothioates and Phosphorodithioates.

An environmentally friendly and resourceful modular protocol for the synthesis of phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates under blue light-emitting diode irradiation is described. The blue LED-promoted P-S, P-Se, and P-Te bond constructions occurred under metal-free, ligand-free, oxidant-free, and photocatalyst-free conditions with minimum chemical waste generation and high atom economy providing the resulting phosphorochalcogenoates, phosphorochalcogenothioates, and phosphinothioates in good to excellent yields.

Carbon-Sulfur Bond Constructions: From Transition-Metal Catalysis to Sustainable Catalysis.

The recent decade evidenced a significant development in the construction of the C-S bond. The journey began with transitional-metal catalysis and reached sustainable catalysis via oxidant, photo, and electro catalyzed methods. A variety of catalytic systems have been explored for the C-S bond formation using a variety of sulfur precursors. This personal account provides an inclusive discussion of these developed methods in terms of reactivity, sustainability and productivity.

Synthesis, Isolation, and Characterization of Mono- and Bis-norbornene-Annulated Biarylamines through Pseudo-Catellani Intermediates.

A palladium-catalyzed C-H functionalization of an external ring of N-acyl 2-aminobiaryl with bicyclo[2.2.1]hept-2-ene (norbornene) via multiple C-H bond activations was developed. This study is the first report of the formation of bis-norbornene annulated biarylamines isomers ( syn-3a'/ anti-3a' = 36:64) from multiple C-H bond functionalizations. Additionally, nondirected C-H bond functionalization at the C-4' position with alkenes rendered complete C-H functionalization of five C-H bonds that formed a stable hexasubstituted benzene ring.

Palladium(II)-Catalyzed Mono- and Bis-alkenylation of N-Acetyl-2-aminobiaryls through Regioselective C-H Bond Activation.

We developed palladium-catalyzed oxidative coupling of olefins with N-acyl 2-aminobiaryls through a sequence of ortho C-H bond activation/alkene insertion/reductive elimination. Furthermore, we controlled the selectivity of mono- and bis-alkenylation products with the solvent effect. The developed protocol was promising for a broad substrate scope ranging from activated olefins with a wide variety of functional groups to unactivated olefins.

Palladium-Catalyzed C-H Bond Activation by Using Iminoquinone as a Directing Group and an Internal Oxidant or a Co-oxidant: Production of Dihydrophenanthridines, Phenanthridines, and Carbazoles.

A palladium-catalyzed C-H bond activation reaction, via a redox-neutral pathway, for the preparation of dihydrophenanthridine, phenanthridine, and carbazole derivatives from biaryl 2-iminoquinones is developed. The preinstalled iminoquinone was designed to act as a directing group for ortho C-H activation and an internal oxidant or a co-oxidant. This catalysis proceeded through the following sequence: C-H bond activation, coordination and insertion of activated olefins, ß-hydride elimination, H-shift, insertion, and protonation or ß-hydride elimination. In addition, carbazoles can be prepared efficiently by using this method without the addition of external oxidants.

Iptycenes with an acridinone motif developed through [4+2] cycloaddition of tethered naphthalene and iminoquinone via a radical reaction.

A new class of iptycenes was developed by combining 2-(naphthalen-1-yl)anilines and p-benzoquinones through copper(ii)-mediated radical cyclisation. This unusual cyclisation reaction resulted in the robust and efficient syntheses of iptycenes with an acridinone motif. These iptycenes can be further transformed into planar acridinone heterocyclics through the Diels-Alder reaction.