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Remote Trifluoromethylthiolation Enabled by Organophotocatalytic Ca??C Bond Cleavage
摘要： The first metal-free ring opening/trifluoromethylthiolation of cycloalkanols for the formation of remote C(sp3)?SCF3 bonds has been developed. A variety of trifluoromethylthiolated carbonyl compounds that are otherwise difficult to achieve were prepared in good yields under mild reaction conditions. The reaction is assumed to proceed via C?C bond cleavage of the alkoxyl radical species generated via a photoredox-enabled intramolecular proton-coupled electron transfer process, followed by trifluoromethylthiolation of the resulting C-centered radical with the N-(trifluoromethylthio)phthalimide reagent.
关键词： trifluoromethylthiolation,C?C bond cleavage,photoredox catalysis,cycloalkanols,alkoxyl radical
更新于2025-09-23 15:19:57
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Photoredox Controlled ?2a??Regioselective Radical Hydroboration of Activated Alkenes with NHCa??Boranes
摘要： In this communication, we report an unprecedented β-regioselective radical inverse hydroboration (compared with ionic hydroboration) of α, β-unsaturated amides with NHC-BH3 enabled by the photoredox catalysis. The density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the β-regioselective radical hydroboration, which makes the energy barrier is lower than other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse β-borylated amides in synthetically useful yields under mild conditions.
关键词： Regioselective hydroboration,Photoredox catalysis,Radical borylation,Umpolung
更新于2025-09-23 15:19:57
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Aerobic α‐Oxidation of N‐Substituted Tetrahydroisoquinolines to Dihydroisoquinolones via Organo‐photocatalysis
摘要： An efficient visible-light-induced α-oxidation of N-substituted tetrahydroisoquinolines to dihydroisoquinolones has been developed using eosin Y as an organo-photocatalyst and oxygen as a green oxidant. The reactions were carried out under mild reaction conditions; the desired dihydroisoquinolones were obtained in up to 96% yield at room temperature under oxygen atmosphere. This transformation provides a convenient route to dihydroisoquinolones with a wide range of substrates.
关键词： photoredox catalysis,lactams,dihydroisoquinolones,aerobic oxidation
更新于2025-09-23 15:19:57
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Decarboxylative Heck Coupling via a Cobalt/Photoredox Catalysis
摘要： The authors report a synthesis of olefins through a photoinduced decarboxylative Heck-type coupling. The method uses alkyl carboxylic acids, which are one of the most ubiquitous building blocks. Based on DFT calculations, a radical mechanism has been proposed. Over 90 examples containing a huge variety of functional groups have been prepared in high yields.
关键词： Heck coupling,cobalt catalysis,photoredox catalysis
更新于2025-09-19 17:15:36
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Metal-free Semiconductor Photocatalysis for sp2 C-H Functionalization with Molecular Oxygen
摘要： Designing metal-free catalysts for solar energy conversion is a long-standing challenge in semiconductor photoredox catalysis (SPC). With visible-light-responsive hexagonal boron carbon nitride (h-BCN) as a non-metal photocatalyst, this system affords C–H/N–H coupling products with broad substitution tolerance and high efficiency with molecular oxygen as the terminal oxidant. The catalyst exhibits remarkable performance for the selective C-H functionalization of electron-rich arenes to C-N products (yields up to 95%) and good stability (6 recycles). Both nitrogen heteroarenes and amine salts are competent coupling nucleophiles. Mechanically, the reactive oxygen species are superoxide anion radical (O2??) and H2O2, which are proved by electron spin resonance (ESR) data, KI-starch, and control experiments. In addition, kinetic isotope effect (KIE) experiments indicate that C–H bond cleavage is not involved in the rate limiting step. This semiconductor-based photoredox system allows for C–H amination free of any metals, ligands, strong oxidants, and additives. It provides a complementary avenue to C–H functionalizations and enables synthetic applications efficiently in a sustainable manner.
关键词： Radical,Semiconductor Photoredox Catalysis,Heterogeneous Catalysis,Visible Light,C-H Fuctionalizaition
更新于2025-09-10 09:29:36
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[Topics in Organometallic Chemistry] || Functionalization of C(sp2)–H Bonds of Arenes and Heteroarenes Assisted by Photoredox Catalysts for the C–C Bond Formation
摘要： The formation of C–C bonds from arenes and heteroarenes through transition metal-catalyzed C–H bond functionalizations is one of the major achievements of these last decades. It is now possible to perform such transformations under mild reaction conditions with the help of visible light photocatalysis leading to eco-friendly and safer process to build organic molecules or materials. This chapter will focus on photoredox catalysis which involves a C(sp2)–H bond functionalization step for the formation of C(sp2)–C bonds [i.e., direct arylations and (per?uoro)alkylations] and will show how this hot topic contributes to the development of green chemistry.
关键词： MLTC photoredox catalysis,C(sp2)–H bond,Visible light,C–C bond formation
更新于2025-09-10 09:29:36
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Enantioselective Allylic Alkylation with 4-Alkyl-1,4-dihydropyridines Enabled by Photoredox/Palladium Cocatalysis
摘要： Highly regio-, and enantioselective allylic alkylation has been achieved enabled by the merger of photoredox and palladium catalysis. In this dual catalytic process, alkyl radicals generated from 4-alkyl-1,4-dihydropyridines act as the coupling partners of the π-allyl palladium complexes. The generality of this method has been illustrated through the reaction of a variety of allyl esters with 4-alkyl-1,4-dihydropyridines. This mechanistically novel strategy expands the scope of the traditional Pd-catalyzed asymmetric allylic alkylation reaction and serves as its alternative and potential complement.
关键词： π-Allyl Palladium Complexes,Palladium Catalysis,4-Alkyl-1,4-dihydropyridines,Photoredox Catalysis,Enantioselective Allylic Alkylation
更新于2025-09-09 09:28:46
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[Topics in Organometallic Chemistry] || Green Cross-Coupling Using Visible Light for C–O and C–N Bond Formation
摘要： The development of green and sustainable approaches in organic synthesis can provide an environmentally friendly method in the industrial manufacture. Recently, visible-light-mediated photocatalysis has achieved great progress and been a powerful tool to the construction of new chemical bonds in the green synthetic community. This chapter provides an updated summary of visible-light-mediated cross-coupling for C–O and C–N bond formations. Compared with the traditional synthetic methods, the visible-light catalysis provides a new way for the useful compounds synthesis (O-containing and N-containing molecules).
关键词： Visible light,C–O bond,Photoredox catalysis,C–H functionalization,Cross-coupling,C–N bond
更新于2025-09-09 09:28:46
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Stereoselective Intermolecular [2+2] Cycloadditions of Erlenmeyer-Pl?chl Azlactones using Visible Light Photoredox Catalysis
摘要： The first report of the preparation of symmetric and non-symmetric diaminotruxinic derivatives through the photoredox [2+2] cycloadditions of Erlenmeyer azlactones is described, affording the desired compounds in high regio- and diastereocontrol (only head-to-head coupling). Mechanistic studies by DFT suggest that the reaction proceeds through a neutral photocatalytic pathway.
关键词： photoredox catalysis,diaminotruxinic derivatives,[2+2] cycloaddition,Erlenmeyer azlactones,DFT studies
更新于2025-09-09 09:28:46
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De novo design of organic photocatalysts: bithiophene derivatives for the visible-light induced C-H functionalization of heteroarenes
摘要： Herein, we report the de novo synthesis and characterization of a series of substituted bithiophene derivatives as novel inexpensive organic photocatalysts. DFT calculations were used to predict a priori their absorption spectra and redox potentials, which were then confirmed with empirical data. The photocatalytic activity of this novel class of organic photoredox catalyst was demonstrated in two visible-light mediated strategies for the C-H functionalization of heteroarenes. The implementation of these strategies in a continuous-flow photo-microreactor afforded moderate to excellent yields within few minutes of reaction time. Due to their straightforward synthesis, low cost and good photocatalytic properties we believe that the proposed bithiophene derivatives could be employed as a new class of organic photoredox catalysts.
关键词： Organic photocatalysts,C-H functionalization,Photoredox catalysis,DFT calculations,Continuous flow catalysis
更新于2025-09-04 15:30:14