Ketone Skeletal Modification via a Metallaphotoredox-Catalyzed Deacylation and Acylation Strategy.

Herein, we describe a dual catalytic strategy that employs dihydroquinazolinones, derived from ketone analogs, as versatile intermediates for acylation via α C-C cleavage with 2-pyridyl esters, facilitating the efficient synthesis of a variety of ketones. The reaction accommodates a wide range of ketones and carboxylic acids, showing tolerance to various functional groups. The versatility of this synthetic technique is further highlighted through its application in the late-stage modification of pharmaceuticals and biologically active natural products.

Base-Mediated α--Difluoroalkenylations of Aldehydes and Ketones.

Herein, we present a base-mediated nucleophilic substitution reaction of α-trifluoromethylstyrenes with simple silyl enol ethers, enabling the efficient synthesis of carbonyl-substituted -difluoroalkenes. The merit of this protocol is exhibited by its mild reaction conditions, broad substrate scope, and scalable preparation. Notably, this method demonstrates its applicability for late-stage functionalization of structurally complex molecules.

Visible-Light Photoredox-Catalyzed Decarboxylative Alkylation of Heteroarenes Using Carboxylic Acids with Hydrogen Release.

Herein, we have developed visible-light photoredox-catalyzed decarboxylating carboxylic acids for alkylation of heteroarenes under mild conditions. The transformation occurred smoothly without the requirement of stoichiometric oxidants in the presence of 0.3 equiv of base, which benefited from the release of hydrogen (H) and carbon dioxide (CO).

Visible-Light Photoredox-Catalyzed Iminyl Radical Formation by N-H Cleavage with Hydrogen Release and Its Application in Synthesis of Isoquinolines.

An unprecedented visible-light photoredox-catalyzed iminyl radical formation by N-H cleavage with H release has been developed. Its application in the synthesis of various isoquinolines and related polyaromatics in high atom economy at ambient temperature by applying a photosensitizer, Acr-Mes ClO, and a new cobalt catalyst, Co(dmgH)(4-CONMePy)Cl is reported. Mechanistic investigations indicated that the generated iminyl radical initiates the cascade C-N/C-C bonds formation and the catalytic cycle occurs by a simultaneous oxidative as well as reductive quenching pathway.

Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis.

Herein, the first acceptorless dehydrogenation of tetrahydroquinolines (THQs), indolines, and other related N-heterocycles, by merging visible-light photoredox catalysis and cobalt catalysis at ambient temperature, is described. The potential applications to organic transformations and hydrogen-storage materials are demonstrated. Primary mechanistic investigations indicate that the catalytic cycle occurs predominantly by an oxidative quenching pathway.

Redox-Divergent Hydrogen-Retentive or Hydrogen-Releasing Synthesis of 3,4-Dihydroisoquinolines or Isoquinolines.

A rare Ru-catalyzed highly selective synthesis of 3,4-dihydroisoquinolines or isoquinolines is accomplished via a redox-divergent hydrogen-retentive or hydrogen-releasing fashion. Notably, high cis-selectivity of 3,4-dihydroisoquinolines is achieved. Potential applications are shown by gram-scale reactions and very concise synthesis of N-containing polycyclic aromatic compounds.

Oxidant-free dehydrogenative coupling reactions via hydrogen evolution.

Oxidant-free dehydrogenative coupling reactions: Recently, coupling reactions have followed a novel strategy for the construction of C==C, C==N, C==P, and S==S bonds by dehydrogenation without using any extra oxidant, via H2 evolution. These breakthroughs inspire a new direction in the construction of chemical bonds, towards more sustainable, highly atom-economical, and environmentally benign synthetic methods.

Synthesis of fluorenone derivatives through Pd-catalyzed dehydrogenative cyclization.

Palladium-catalyzed dual C-H functionalization of benzophenones to form fluorenones by oxidative dehydrogenative cyclization is reported. This method provides a concise and effective route toward the synthesis of fluorenone derivatives, which shows outstanding functional group compatibility.

Straightforward synthesis of phenanthrenes from styrenes and arenes.

Semi-one-pot synthesis of phenanthrenes from styrenes and arenes was developed through cross-dehydrogenative coupling. A sequence of Heck-type coupling and photo-cyclization were involved and a variety of functionalities were tolerated. This method provides an effective and practical protocol towards the synthesis of substituted phenanthrenes.

N-Directing group assisted rhodium-catalyzed aryl C-H addition to aryl aldehydes.

Direct aryl C-H addition to aryl aldehydes to produce biaryl methanols was reported via Rh catalysis with an N-containing directing group. The method is highly atom-, step-, and redox-economic. The procedure is robust, reliable, and compatible with water and air.