Domino Conjugate Addition-1,4-Aryl Migration for the Synthesis of α,β-Difunctionalized Amides.

A domino difunctionalization of sulfonyl(acryl)imides to form β-substituted α-aryl amides is reported. This transformation involves a 1,4-addition followed by a polar Truce-Smiles rearrangement process, entropically driven by release of SO. A wide range of carbon- and heteroatom-based nucleophiles and sulfonyl imides were employed, allowing rapid access to highly functionalized amides.

Photocatalytic (3 + 2) dipolar cycloadditions of aziridines driven by visible-light.

Herein, we document the design and development of a novel (3 + 2) cycloaddition reaction aided by the activity of an organic photocatalyst and visible light. The process is extremely fast, taking place in a few minutes, with virtually complete atom economy. A large variety of structurally diverse aziridines were used as masked ylides in the presence of different types of dipolarophiles (28 examples with up to 94% yield and >95 : 5 dr).

A General Organophotoredox Strategy to Difluoroalkyl Bicycloalkane (CF2-BCA) Hybrid Bioisosteres.

Here, we report a general approach to the synthesis of the difluoroalkyl bicycloalkanes (CF -BCAs), as structural surrogates of aryl ketones and ethers. The chemistry is driven by a dihydrobenzoacridine photocatalyst, that engages in a catalytic electron-donor acceptor (EDA) complex, or directly reduces the fluorinated substrate. These two convergent manifolds lead to the generation of the R-CF radical, that reacts with the [1.

The Rational Design of Reducing Organophotoredox Catalysts Unlocks Proton-Coupled Electron-Transfer and Atom Transfer Radical Polymerization Mechanisms.

Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine transformations. However, only a handful of versatile organic photocatalysts (PCs) are available, hampering the discovery of new reactivities. Here, we report the design and complete physicochemical characterization of 9-aryl dihydroacridines (9ADA) and 12-aryl dihydrobenzoacridines (12ADBA) as strong reducing organic PCs.

Modern Photocatalytic Strategies in Natural Product Synthesis.

Modern photocatalysis has proven its generality for the development and functionalization of native functionalities. To date, the field has found broad applications in diverse research areas, including the total synthesis of natural products. This contribution covers recent reports of total syntheses involving as a key step a photocatalytic reaction.

The advent and development of organophotoredox catalysis.

In the last decade, photoredox catalysis has unlocked unprecedented reactivities in synthetic organic chemistry. Seminal advancements in the field have involved the use of well-studied metal complexes as photoredox catalysts (PCs). More recently, the synthetic community, looking for more sustainable approaches, has been moving towards the use of purely organic molecules.

Radical α-Trifluoromethoxylation of Ketones under Batch and Flow Conditions by Means of Organic Photoredox Catalysis.

The first light-driven method for the α-trifluoromethoxylation of ketones is reported. Enol carbonates react with -trifluoromethoxy-4-cyano-pyridinium, using the photoredox catalyst 4-CzIPN under 456 nm irradiation, affording the α-trifluoromethoxy ketones in ≤50% isolated yield and complete chemoselectivity. As shown by 29 examples, the reaction is general and proceeds very rapidly under batch (1 h) and flow conditions (2 min).