A protocol for the photooxidative activation of α-silylamines and α-amino acids desilylative decarboxylative additions, allylations, heteroarylations in presence graphitic carbon nitride (g-C3N4) was developed. The procedure has broad scope provides desired products high yields. heterogeneous nature g-C3N4 catalytic system enables easy recovery recycling as well use multiple runs without loss activity. photoredox catalyzed reactions can also be conducted continuous photo flow fashion scaled...

Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source readily accessible benzophenone derivatives photosensitisers has been developed in batch flow. The use an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.

A practical protocol for hydrotrifluoromethylthiolation of diazo compounds has been developed. range in combination with a nucleophilic SCF3 source provided access to valuable trifluoromethylthiolated compounds. Furthermore, methodology the first double trifluoromethylthiolation was

A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts an iridium photocatalyst. The reactivity has been evaluated for functionalization a variety activated olefins.

α-Amino acids are among the most common biologically active molecules in nature, and their functionalization has attracted much attention. In this communication, a novel, efficient general visible-light photocatalytic decarboxylative monofluoroalkenylation of N-protected α-amino with gem-difluoroalkenes is reported, affording corresponding monofluoroalkenes which might find applications medical chemistry materials science. The reaction proceeded at room temperature high efficiency tolerance...

A mild approach for the decarboxylative aminomethylation of aryl sulfonates by combination photoredox and nickel catalysis through C-O bond cleavage is described first time. wide range triflates as well mesylates, tosylates alkenyl afford corresponding products in good to excellent yields.

Bridged or caged polycyclic hydrocarbons have rigid structures that project substituents into precise regions of 3D space, making them attractive as linking groups in materials science and building blocks for medicinal chemistry. The efficient synthesis new underexplored classes such compounds is, therefore, an important objective. Herein, we describe the silver(I)-catalyzed rearrangement 1,4-disubstituted cubanes to cuneanes, which are strained not received much attention since they were...

The aerobic, room-temperature coupling of tetramethylammonium trifluoromethylselenate with readily available boronic acids, esters, and terminal alkynes has been developed. method permits direct access to valuable trifluoromethylselenoarenes under mild conditions. A convenient one-pot reaction, a scale up procedure as well an extension perfluoroalkylselenates are also presented further demonstrate the synthetic utility this reaction.

We present α-chloro amides as a new class of α-acetyl radical precursors, which undergo tin-free, photoredox-catalysed intermolecular α-alkylation with various olefins exclusively in an anti-Markovnikov fashion. The reaction represents reductive atom transfer addition (ATRA) and provides series alkylated good yields.

Analogues of dibenzodiazepines, in which the seven-membered nitrogen heterocycle is replaced by a 9-12-membered ring, were made an unactivated Smiles rearrangement five- to eight-membered heterocyclic anthranilamides. The conformational preference tertiary amide starting material leads intramolecular migration range aryl rings, even those lacking electron-withdrawing activating groups, and provides method for n→n+4 ring expansion. medium-ring products adopt chiral ground state with...

Take it slow! A metal-organic container molecule has been shown to bind guanidinium cations (blue) between the sulfonate groups on its periphery, as well accommodating guests such cyclopentane and cyclohexane in internal cavity (red). Kinetic studies system demonstrated a linear relationship amount of bound ions rate guest exchange.

The direct alkylation of imines with redox-active esters by visible light photoorganocatalysis provides a way for accessing α-branched secondary amines which are found in numerous bioactive molecules.

Enantioselective amine-catalyzed conjugate additions of aldehydes to oxetane- and azetidine-containing nitroolefins afford γ-nitroaldehydes as key building blocks en route spirocyclic oxetane/azetidine-pyrrolidines. The study provided insights into the stability reactivity these β,β-disubstituted enabled enantioselective synthesis chiral oxetanes azetidines in moderate-to-high yields enantioselectivities. This approach expands synthetic access medicinally relevant scaffolds broadens scope...

Bicyclo[2.1.1]hexane is an emerging scaffold in various pharmaceutical settings, but the scarcity of approaches to target different regioisomers from a common starting material prevents targeting broader range chemical space. Herein, we demonstrate new design for photocatalyst-controlled regiodivergent synthesis this scaffold. Of particular interest that two distinct substitution patterns was achieved under photochemical conditions with catalyst control. This possible due activating group,...

Direct trifluoromethylation of organic molecules is upmost importance in medicinal chemistry and agrochemical research. However, finding sustainable reaction conditions should be a priority for chemists to improve the applicability their Herein, we highlight recent advances transition-metal-free photochemical activation sodium triflinate, commercially available easy-to-handle source CF₃ radical. 1. Introduction 2. Transition-Metal-Free Activation Sodium Triflinate 3. Photochemical...

Tetrahydroisoquinolines and tetrahydrobenzazepines were prepared by acid-promoted ring contraction of cyclic ureas, which themselves formed expansion indolines tetrahydroquinolines. The consequent overall one-carbon insertion reaction gives these 6- 7-membered heterocyclic scaffolds in three steps from readily available precursors. Other sizes may be an alternative elimination bicyclic structures. Scalability the method was demonstrated operating it a flow system.

A continuous flow oxidative photocyclization of stilbene derivatives has been developed which allows the scalable synthesis backbone functionalized phenanthrenes and helicenes various sizes in good yields.

Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox-neutral azocycloamination. In general, N-aryl O-prenyl cyclize in a photocatalytic reaction visible light an organic dye. With electron-deficient diazonium electronic matching electron-rich substituent results proceeding the ground state, without either or photocatalyst. Cyclic voltammetry suggests that this radical is initiated by hydrogen-atom abstraction mediated aryl radical, followed addition cascade...

Abstract Analogues of dibenzodiazepines, in which the seven‐membered nitrogen heterocycle is replaced by a 9–12‐membered ring, were made an unactivated Smiles rearrangement five‐ to eight‐membered heterocyclic anthranilamides. The conformational preference tertiary amide starting material leads intramolecular migration range aryl rings, even those lacking electron‐withdrawing activating groups, and provides method for n → +4 ring expansion. medium‐ring products adopt chiral ground state with...

The base-promoted dearomatizing cyclization of anionic indole-containing urea derivatives provided tri- or tetracyclic indoline-containing scaffolds from lithiated intermediates. 3-Substituted indoles, including tryptamine derivatives, generally underwent the reaction in high yield and with excellent diastereoselectivity. In situ IR spectroscopy suggests a deprotonation–carbolithiation–reprotonation mechanism.

Abstract Owing to their wide range of biological properties, γ‐aminobutyric acid derivatives (GABA) have been extensively studied and found noteworthy industrial applications. However, atom‐economical efficient processes for production are scarce would greatly benefit from further investigations. Herein, we demonstrate that an iridium‐based photocatalyst promotes the direct reductive cross‐coupling imines with olefins upon irradiation visible light give GABA in good yields selectivities. We...

Einlasskontrolle: Ein Metall-organisches Containermolekül bindet Guanidiniumkationen (blau) zwischen den Sulfonatgruppen an seiner Peripherie und nimmt Gastmoleküle wie Cyclopentan Cyclohexan in seinem Hohlraum (rot) auf. Kinetikstudien ergeben eine lineare Beziehung der Menge gebundenen Guanidiniumionen Geschwindigkeit des Gast-Austauschs. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or...

Carbon-carbon double bond (C=C) formation is a crucial transformation in organic chemistry. Visible-light photoredox catalysis provides economical and sustainable opportunities for the development of novel peculiar reactions. Here we report method olefination alkyl halides with aldehydes by visible-light using triphenylphosphine as reductive quencher (103 examples). This accommodates variety including paraformaldehyde; aqueous formaldehyde; 2,2,2-trifluoroacetaldehyde monohydrate;...

Abstract Tetrahydroisoquinolines and tetrahydrobenzazepines were prepared by acid‐promoted ring contraction of cyclic ureas, which themselves formed expansion indolines tetrahydroquinolines. The consequent overall one‐carbon insertion reaction gives these 6‐ 7‐membered heterocyclic scaffolds in three steps from readily available precursors. Other sizes may be an alternative elimination bicyclic structures. Scalability the method was demonstrated operating it a flow system.

Bioisosteric replacement is an indispensable tool in the medicinal chemist’s arsenal to strike a fine balance multiparameter optimization campaigns and deliver best molecules for further preclinical development. The piperidine heterocycle, dominant fragment drug discovery, often targeted such attempts improve potency ADME (absorption, distribution, metabolism, excretion) profile. In this manuscript we explore 4H-Dewar pyridines (4H-DP) as rigid programmable isosteres of equatorially elusive...