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 stoichiometric oxidants in presence 0.3 equiv base, which benefited from release hydrogen (H2) and carbon dioxide (CO2). Various substrates functional groups were tolerated. Primary mechanistic studies suggest that an oxidative quenching pathway a reductive are both possible catalytic cycle.

Cleavage of C-O bonds in lignin can afford the renewable aryl sources for fine chemicals. However, high bond energies these bonds, especially 4-O-5-type diaryl ether (~314 kJ/mol) make cleavage very challenging. Here, we report visible-light photoredox-catalyzed ethers by an acidolysis with carboxylic acid and a following one-pot hydrolysis. Two molecules phenols are obtained from one molecule at room temperature. The used be recovered. key to success is merging photoredox catalysis using...

Abstract An efficient synthesis of 2‐substituted quinolines from readily available cyclopropanols and imidamides has been developed, where the cyclopropanol acts as a C 3 synthon. With assistance bifunctional imidamide directing group, reaction occurred via sequential C–H/C–C cleavage C–C/C–N bond formation. magnified image

A new method for conducting a reductive alkylation/arylation of 1,2-diketones using visible light and unactivated organic halides is presented in this article. This technique does not require photocatalyst employs Et3N, tertiary amine, as promoter. amine aids generating ketyl radical an α-aminoalkyl radical, which engages C-X bond activation via halogen atom transfer process (XAT). approach's success hinges on utilizing Et3N the article's mild straightforward protocol allows significantly...

An unprecedented visible-light photoredox-catalyzed iminyl radical formation by N–H cleavage with H2 release has been developed. Its application in the synthesis of various isoquinolines and related polyaromatics high atom economy at ambient temperature applying a photosensitizer, Acr+-Mes ClO4–, new cobalt catalyst, Co(dmgH)2(4-CONMe2Py)Cl is reported. Mechanistic investigations indicated that generated initiates cascade C–N/C–C bonds catalytic cycle occurs simultaneous oxidative as well...

Abstract Manganese (Mn) is the third most abundant transition metal on Earth and known for its exceptional biocompatibility. The development of novel catalytic mode Mn great significance to advancing organic synthesis. In this study, first manganese (Mn)‐catalyzed [2+2+2] cycloaddition alkynes achieved with aid visible‐light photoredox catalysis. Photoredox catalysis proposed promote transformation by in situ reduction high‐valent Mn(II) complex Mn(0) species, thereby initiating reaction....

Abstract A hydroxyl‐assisted, organophotoredox/cobalt dual catalyzed annulation of 2‐propynolphenols to form 2‐hydroxymethyl‐benzo[ b ]furans was developed by employing 1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene (4CzIPN) as photosensitizer and CoCl 2 (PPh 3 ) /5,5′‐dimethyl‐2,2′‐bipyridine cobalt catalytic precursor. Various substrates functional groups were tolerated. The practical applications this reaction further demonstrated enlarged gram‐scale various derivations for complex...

Abstract Herein, the first example of visible‐light‐driven, cobalt‐catalyzed transfer semihydrogenation alkynes to alkenes is reported. It carried out by using Ir[dF(CF 3 )ppy] 2 (dtbbpy)]PF 6 as photosensitizer, CoBr / n ‐Bu P proton‐reducing catalyst, and i ‐Pr NEt/AcOH hydrogen source. Under established catalytic system, proceeds with Z major selectivity inhibition over‐reduction. mild reaction conditions, both internal terminal alkynes, well reducible functional groups such halogen,...

A general and metal-free protocol for the construction of benzo[b]fluorenyl thiophosphates was developed through cascade cyclization easily prepared diynols (RO)2P(O)SH, with water as only byproduct. The novel transformation involved allenyl thiophosphate key intermediate, followed by Schmittel-type to achieve desired products. Notably, (RO)2P(O)SH acted not a nucleophile but also an acid-promoter initiate reaction.

Herein, a highly regioselective alkylation of propargylic carbonates for trisubstituted allenes with alkyl 1,4-dihydropyridine derivatives (1,4-DHPs) is developed via photoredox/nickel dual-catalyzed process, which represents the first direct approach to access alkylated allene products without organometallic reagents. This method features broad substrate scope and mild conditions. A hypothetical mechanism an radical allenyl Ni(III) species proposed. Benzylation were also obtained be...

A visible-light enabled, chemoselective photoreduction of 1,2-dicarbonyl compounds by using Hünig's base as reductant is reported.

Abstract A novel protocol of Iodine catalyzed oxidative 3‐sulfenylation indoles with thiols has been developed using cheap and environment friendly Hydrogen peroxide (30 % H 2 O ) as oxidant. In addition, was firstly used solvent in this type reaction, method, react multiple smoothly various 3‐sulfanylindoles were obtained good to excellent yields.. The extensive scope substrates, the mild reaction conditions, high selection site delivery promising applications drug discovery functional...

The first photo-induced nickel-mediated regioselective radical–radical cross-electrophile coupling process with alkyl NHP esters and EDA complexes for alkylated allenes is described.

Abstract An efficient and facile protocol concerning Cu(II)‐catalyzed methylthiolation of 8‐aminoquinoline amides under air atmosphere with widely available DMSO as the terminal thiomethyl source has been developed. The reaction exhibits excellent functional group tolerance highly regioselectivity, which provides an attractive approach for aryl methyl thioethers preparation.

Abstract Herein, a hydroxyl assisted, photoredox/cobalt co‐catalyzed semi‐hydrogenation and tandem cyclization of o ‐alkynylphenols is developed towards direct assembly 2,3‐dihydrobenzofurans. Moderate to good yields were obtained for range sterically electronically diverse 2‐propynolphenols under mild conditions. Mechanistic studies demonstrated the inevitable role alcoholic group with (Z)‐alkene as real intermediate. Finally, key low‐valent cobalt catalyzed intramolecular...

The synthesis of the enantiomerically pure, D3-symmetric covalent hydrocarbon cages (+)-(M,M)-4 and (−)-(P,P)-4 bearing two C3-symmetrically functionalized tribenzobenzotriquinacene (TBTQ) vertices is reported. pure TBTQ building blocks (+)-(M)-5 (−)-(P)-5 were prepared via diastereomeric triamides obtained by use both Boc-d- Boc-l-phenylglycine as chiral auxiliaries.

The first allenylic alkylation with non-activated aliphatic amine derivatives, Katritzky salts, has been developed via photoredox/nickel dual-catalyzed reductive deaminative cross-electrophile coupling.

Through a surprisingly nonregioselective oxidation process, the reaction of two analogous 2-hydroxy-substituted tribenzotriquinacenes (TBTQs) 8a/8b by o-iodoxybenzoic acid was found to afford corresponding Cs- and C1-symmetrical TBTQ-o-quinones 6a/6b 7a/7b, respectively, in 1:1 ratio excellent combined yields. This finding represents first example direct introduction functional group into sterically hindered, inner bay-positions parent TBTQ skeleton. In contrast, with 1-hydroxy-TBTQ 15...

The wavelength-regulated, photoredox-catalyzed stereodivergent synthesis of ( Z )- and E )-1,4-enediones from phosphonium ylides is reported.

Abstract An efficient and practical approach for the synthesis of triaryl allenyl sulfones from easily accessible propargylic alcohols was developed, by using sodium sulfinates as a sulfonyl source in presence Brønsted acid. The reaction proceeded via carbocation key intermediate followed nucleophilic attack to produce moderate excellent yields.

Abstract Herein, we report a highly efficient Sonogashira‐type cross‐coupling reaction of heteroaryl halides with terminal alkynes under mild transition‐metal‐free conditions using PPh 3 and Cs 2 CO /NEt , A wide range functional groups was tolerated optimized conditions. Furthermore, the protocol could be extended to Suzuki‐type phenylboronic acid, achieving corresponding products in good excellent yields. test on gram scale delivered product reasonably high yield thus has potential...

Abstract A practical and environmentally friendly approach is presented for the efficient construction of propargyl organothiophosphates allenyl from easily prepared secondary propargylic alcohols O , ‐diethyl phosphorothioic acid [(EtO) 2 P(O)SH]. The reaction proceeds smoothly in moderate to excellent yields without additional promoters or additives under mild conditions with water as only by‐product. divergent products are selectively obtained depending on substrates bearing different...

An unexpected Ir/Co dual catalytic hydroacylation of electron-deficient alkenes overcoming redox potential limitations is reported.

In this work, a photo-driven thiol-free phosphine/D2O-mediated method was developed for the reductive deuteration of pyridyl ketones. By regulating reaction conditions, site-selective diketone achieved in high deuterium incorporation rates.