The introduction of thianthrene as a linchpin has proven to be versatile strategy for the C–H functionalization aromatic compounds, featuring broad scope and fast diversification. synthesis aryl thianthrenium salts displayed an unusually high para regioselectivity, notably superior those observed in halogenation or borylation reactions various substrates. We report experimental computational study on mechanism thianthrenation reactions, with emphasis elucidation reactive species nature...

Aryldiazonium salts remain a staple in organic synthesis and are still prepared largely accord with the protocol developed 19th century. Because of favorable reactivity that often cannot be achieved other aryl(pseudo)halides, diazonium chemistry continues to grow. Facile extrusion dinitrogen contributes desired but is also reason for safety concerns. Explosions have occurred since discovery these reagents result accidents. In this study, we report paradigm shift based on nitrate reduction...

Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited-state potentials, PC*/PC.- 1.65 V) PC.+ /PC* -1.77 V vs. SCE), are such these novel PCs can engage in both oxidative reductive quenching mechanisms with strong thermodynamic requirements. The potential of bimodal was benchmarked...

A scalable visible-light [2 + 2]-heterocycloaddition process allows the dearomatisation of indoles to complex biorelevant polycycles.

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

Abstract Organic photocatalysts are emerging as viable and more sustainable tools than metal complexes. Recently, the field of organo‐photocatalysis has experienced an explosion in terms applications, redesign well‐established systems, identification novel scaffolds. A rational approach to structural modification different is key accessing unprecedented reactivity, while improving their catalytic performances. We herein discuss concepts underpinning scaffold some most recently used analyze...

Halloysite nanotubes can be used for the preparation of solid catalysts. Owing to their natural availability at low-cost as well large and easy-to-functionalize surface, they conveniently activated with mineral acids or derivatized acidic groups. Nevertheless, use HNTs catalysts in complex transformations is still limited. Herein, we report two strategies utilize HNT-based materials Biginelli reaction. To this aim, methods increasing number sites on were explored: (i) treatment piranha...

Light-driven reactions of 2-methylbenzophenones (2-MBPs) occur with improved yields (up to >98%) and reaction rates 0.240 mmol h-1) by using a tailored microfluidic photoreactor (MFP). For the first time, coumarins were converted into 4-benzylated chromanones in high (50-93%) diastereoselectivity >20 : 1 dr), thus by-passing their photo-dimerisation end-reaction.

The exploitation of an intermolecular Si–F interaction between the substrates, together with chiral Lewis-base catalysis, allows regio-, diastereo- and enantioselective allylation ketone-derived silyl enol ethers allyl fluorides.

A novel microfluidic visible‐light process for the functionalisation of oxindoles is reported. The chemistry based on reactivity corresponding enol ethers, which participate in a site‐, regio‐ and diastereoselective [2+2] heterocycloaddition (Paternò–Büchi) process. mild reaction conditions, use available ketones, together with high generality (23 examples) robustness (up to gram scale) make this useful synthetic platform construction structurally strained heterocycles.

Abstract In this Account, we summarize the contributions of our group to field photochemistry and photocatalysis. Our work deals with development novel synthetic methods based on exploitation photoexcited aryl ketones. The application new technologies, such as microfluidic photoreactors (MFPs), has enhanced performance scalability several photochemical methods, e.g., Paternò–Büchi photoenolization/Diels–Alder processes, while opening way unprecedented reactivity. addition, careful...

Herein we report an effective synthetic method for the direct assembly of highly functionalized tetracyclic pharmacophoric cores. Coumarins and chromones undergo diastereoselective [4 + 2] cycloaddition reactions with light-generated photoenol intermediates. The occur by aid a microfluidic photoreactor (MFP) in high yield (up to >98%) virtually complete diastereocontrol (>20:1 dr). is easily scaled-up parallel setup, furnishing 948 mg product over 14 h reaction time. Finally, series...

Abstract Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited‐state potentials, PC*/PC .− 1.65 V) PC .+ /PC* −1.77 V vs. SCE), are such these novel PCs can engage in both oxidative reductive quenching mechanisms with strong thermodynamic requirements. The potential of bimodal was...

The stereocontrolled installation of alkyl fragments at the alpha position ketones is a fundamental yet unresolved transformation in organic chemistry. Herein we report new catalytic methodology able to construct alpha-allyl via defluorinative allylation silyl enol ethers regio- diastereo- and enantioselective manner. protocol leverages unique features fluorine atom simultaneously act as leaving group activate fluorophilic nucleophile SiF interaction. A series spectroscopic, electroanalytic...

The metal complex formed by coordination of Zn II to 1,7‐bis(4‐methylpyridine)‐4‐(2‐naphthylmethyl)‐1,4,7‐triazaheptane ( ZnL 2+ ) was reacted in aqueous solution with [Pd(NO 3 2 (en)] and [Pt(NO salts form the self‐assembled heterometallic macrocycles [Zn L Pd (en) ] 8+ Pt , respectively. ‐coordination modulates original emission arising from presence naphthalene chromophore formation can be monitored due PET process occurring pyridine units . Additionally, several studies reveal that these...

A large variety of highly functionalized N-containing polycycles (35 examples) are synthetized from simple indoles and aromatic ketones through a mild visible-light-driven [2+2]-heterocycloaddition process. Tetrahydrooxeto[2,3b]indole scaffolds, with up to three contiguous all-substituted stereo-centers generated in high yield (up >98%) excellent site- regio- diastereocontrol (>20:1). The use visible light (405 or 465 nm) ensures enhanced performances by switching off undesired...

A large variety of highly functionalized N-containing polycycles (35 examples) are synthetized from simple indoles and aromatic ketones through a mild visible-light-driven [2+2]-heterocycloaddition process. Tetrahydrooxeto[2,3b]indole scaffolds, with up to three contiguous all-substituted stereo-centers generated in high yield (up >98%) excellent site- regio- diastereocontrol (>20:1). The use visible light (405 or 465 nm) ensures enhanced performances by switching off undesired...