A redox-neutral intermolecular dicarbofunctionalization of styrenes with CO2 at atmospheric pressure and carbon-centered radicals is described. This mild protocol results in multiple C-C bond-forming reactions from simple precursors the absence stoichiometric reductants, thus exploiting a previously unrecognized opportunity that complements existing catalytic carboxylation events.

54 years later: Saturated imidazolidin-2-ylidenes react with aldehydes to smoothly produce the elusive 2,2-diamino enols A ("Breslow intermediates", first postulated in 1958) of carbene-catalyzed umpolung reactions. The additional aldehyde a cross-benzoin reaction. methylated Breslow intermediates B are accessible by deprotonation methoxymethyl azolium salts. Detailed facts importance specialist readers published as "Supporting Information". Such documents peer-reviewed, but not copy-edited...

Caught in the act: Diamino enols, diamino dienols, azolium enolates, and enols are postulated intermediates of N-heterocyclic carbene catalyzed umpolung aldehydes enals. Several these elusive reaction were generated with saturated imidazolidin-2-ylidene SIPr (R=2,6-bis(2-propyl)phenyl) characterized by NMR spectroscopy X-ray crystallography.

A Ni-catalyzed reductive deaminative arylation at unactivated sp3 carbon centers is described. This operationally simple and user-friendly protocol exhibits excellent chemoselectivity profile broad substrate scope, thus complementing existing metal-catalyzed cross-coupling reactions to forge C–C linkages. These virtues have been assessed in the context of late-stage functionalization, hence providing a strategic advantage reliably generate structure diversity with amine-containing drugs.

No more substrate restrictions! Cerium photocatalytic decarboxylative hydrazination of carboxylic acids yields synthetically useful hydrazine derivatives under mild reaction conditions.

An efficient, catalyst- and additive-free, visible-light-driven radical C3-H alkylation of quinoxalin-2(1H)-one derivatives has been developed. This reaction utilizes alkyl-NHP-esters as an alkyl donor acceptor. The operationally simple protocol works under mild conditions tolerates a variety functional groups. Furthermore, the synthetic utility methodology was successfully implemented for synthesizing biologically relevant C3-alkyl substituted derivatives.

We report herein that photoinduced CO2•– enabled reductive intramolecular radical cyclization of a variety aryl iodide derivatives to the corresponding phenanthridinone, oxindole, isoindolinone, and spirolactam in good yields. Preliminary mechanistic studies suggested generation through homolysis cesium formate presence light, further involvement was directly proved by trapping with diphenyl styrene TEMPO.

Abstract A redox‐neutral intermolecular dicarbofunctionalization of styrenes with CO 2 at atmospheric pressure and carbon‐centered radicals is described. This mild protocol results in multiple C−C bond‐forming reactions from simple precursors the absence stoichiometric reductants, thus exploiting a previously unrecognized opportunity that complements existing catalytic carboxylation events.

Abstract In the early days of synthetic organic chemistry Hantzsch esters (HEs) were bio‐inspired hydride donors and often used for reduction C=X (X=C, N, O) bonds. Recently, it has been proved that HEs their derivatives (4‐Alkyl‐ or acyl‐Hantzsch esters) serve as electron donor, proton source, hydrogen atom alkyl acyl radical precursors in photoredox catalysis. Recently was found excited‐state also identified a strong photo reductant absence photocatalyst also, donor HE forms EDA‐complexes...

54 Jahre später: Durch Reaktion von gesättigten Imidazolidin-2-ylidenen mit Aldehyden werden 2,2-Diaminoenole A („Breslow-Intermediate“, 1958 postuliert), generiert, die Schlüsselintermediate in carbenkatalysierten Umpolungsreaktionen sind. Die reagieren weiterem Aldehyd einer gekreuzten Benzoinkondensation. methylierten Breslow-Intermediate B sind durch Deprotonierung Methoxymethylazolium-Salzen zugänglich. Detailed facts of importance to specialist readers are published as ”Supporting...

As reported by Scheidt and Bode in 2005, sterically nonencumbered α,β-enals are readily converted to saturated esters the presence of alcohols N-heterocyclic carbene catalysts, e.g., benzimidazolylidenes or triazolylidenes. However, substituents at α- β-position α,β-enal substrate typically not tolerated, thus severely limiting spectrum. On basis our earlier mechanistic studies, a set N-Mes- N-Dipp-substituted 1,2,4-triazolium salts were synthesized evaluated as (pre)catalysts redox...

The first cerium photocatalyzed dehydrogenative lactonization of 2-arylbenzoic acids has been developed. This operationally simple protocol allows rapid access to synthetically useful coumarins on gram scale by employing CeCl3 as a photocatalyst and O2 terminal oxidant. Overall, this delivers an economical environmentally amiable entry diversely substituted coumarins, important structural motifs in bioactive molecules.

Auf frischer Tat ertappt: Diaminoenole, Diaminodienole, Azoliumenolate und Azoliumenole sind postulierte Intermediate in durch N-heterocyclische Carbene katalysierten Umpolungen von Aldehyden Enalen. Mehrere dieser schwer fassbaren Spezies wurden aus dem gesättigten Imidazolidin-2-yliden SIPr (R = 2,6-Bis(2-propyl)phenyl) erzeugt NMR-Spektroskopie Kristallstrukturanalyse charakterisiert. As a service to our authors and readers, this journal provides supporting information supplied by the...

NMR/X-ray evidence is provided for hitherto postulated reactivity patterns of homoenolate <italic>vs.</italic> azolium enolate intermediates in NHC-catalyzed umpolung enals.

PPh₃/NaI driven photocatalytic decarboxylative cyclization of 2-isocyanobiaryls with alkyl NHP esters was developed. This simple protocol afforded a novel and environmentally friendly approach to furnish 6-alkyl phenanthridines in good yields.

We herein report the first visible-light-mediated cross-coupling of unactivated alkyl iodides with aryl bromides through synergistic halogen atom transfer (XAT) and nickel catalysis. This simple protocol operates under mild reaction conditions tolerates a variety functional groups affording C(sp3)–C(sp2) products in good to moderate yields.

Herein, we demonstrate the synthesis and characterization of bench stable tri/difluoromethylating reagents their potential applications in redox neutral hydro tri/difluoromethylation alkenes enabled by visible light. The new are obtained on a gram-scale through simply cyclocondensation commercially available anthranilamide with phenyltrifluoro or difluoromethyl ketone. Preliminary mechanistic studies indicated that canonical photoredox catalytic cycle is being operative. DFT support this...

Herein, we report the first metal-free, redox-neutral strategy for radical cascade alkylative addition, cyclization of N-arylacrylamides with unactivated alkyl chlorides to give corresponding 3,3-disubstituted oxindoles in moderate good yields. This transformation's salient features are utilization an organo photocatalyst, mild reaction conditions, and broad substrate scope. Moreover, this methodology is suitable hetero cycle derived acrylamides further allowed utilize aryl reaction....

In the present manuscript, we reported first visible-light-enabled direct C3-H alkylation/arylation of quinoxalin-2(1H)-ones with unactivated alkyl/aryl chlorides under metal-free conditions. A wide range alkyl and aryl containing different functionalities are coupled a variety quinoxalin-2(1H)-one derivatives mild reaction conditions to afford C3-alkyl/aryl substituted in moderate good yields.

In this work, we developed a general catalytic strategy that allows Minisci C-H alkylation of variety heterocycles using unactivated alkyl halide as an radical source under visible light photocatalysis. Mild reaction conditions, employing 4CzIPN organophotocatalyst and aerial oxygen green terminal oxidant, broad scope, good functional group tolerance, late-stage bioactive pharmaceutically relevant molecules are advantages the protocol. Preliminary mechanistic studies indicate involvement...

Herein, we developed alkyl radical generation from C(sp3)–H bonds of alkanes via a photoinduced HAT-process without employing an external metal, photocatalyst, and organic peroxide. The generated participates in addition cascade cyclization N-arylacrylamides/N-acryloyl benzamides to deliver structurally diverse valuable functionalized oxindoles isoquinolinediones moderate good yields. Preliminary mechanistic studies indicated the aryl through homolytic cleavage Ar–I direct photoexcitation iodide.

We report herein, a simple method for hydroalkylation of 3-methyleneisoindolin-1-ones with unactivated iodoalkanes using visible light photocatalysis and halogen atom transfer (XAT) process. This operationally exhibits broad substrate...

Due to their versatility and stability, alkylboronic acids derivatives have emerged as valuable reagents in organic synthesis, particularly radical chemistry for constructing diverse carbon‐carbon carbon‐heteroatom bonds. Recent advancements expanded applications, enabling the generation of alkyl radicals under milder conditions, safely cost‐effectively. This mini‐review focuses on recent advances methods by which are generated from derivatives, with a special focus reaction mechanism...

We herein report a simple protocol for metal-free cross-coupling between unactivated alkyl iodides and terminal alkynyl bromides promoted by visible light. The salient features of this transformation are the utilization an organic photocatalyst commercially available tri-n-butylamine as reductant. This couples variety iodoalkanes containing different functional groups with under mild reaction conditions to afford substituted alkynes in good yields.

Abstract Herein, we developed a photoinduced remote selective C( sp 3 )−H alkylation of protected amines in the presence cesium formate. The were synthesized from commercially available inexpensive 2‐iodo benzoyl chloride. Under mild reaction conditions, situ generated aryl radical is converted to α‐amidoalkyl via [1,5]‐HAT process, which combines with different Michael acceptors and affords corresponding products good yields. Preliminary mechanistic studies revealed that formate anion acts...