Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of visible photon (&gt;4.0 V <italic>vs.</italic> SCE) in anti-Kasha photo(electro)chemical super-oxidations arenes.

A Rh(III)-catalyzed o-C-H bond functionalization-based allenylation reaction of allenylsilanes 2 with N-methoxybenzamides 1 affords poly-substituted a wide range attractive functional groups in moderate to excellent yields under very mild conditions (20 °C, compatible ambient air and moisture). Those products may be transformed different structural features. Careful mechanistic studies suggest the proceeds via o-rhodation, regioselective insertion, β-H elimination.

Enantioselective synthesis of fully substituted allenes has been a challenge due to the non-rigid nature axial chirality, which spreads over three carbon atoms. Here we show commercially available simple Rh complex may catalyse CMD (concerted metalation/deprotonation)-based reaction readily arenes with sterically congested tertiary propargylic carbonates at ambient temperature affording allenes. It is confirmed that excellent designed regioselectivity for C-C triple bond insertion induced by...

A Rh(iii) catalyzed formal [4 + 2 2] cyclization of N-pivaloyloxybenzamides 1 with 1,6-allene-enes by C-H functionalization is reported. The reactions occur at room temperature and are compatible air moisture a tolerance many synthetically useful functional groups. follow-up modifications the products have been demonstrated. After careful mechanistic studies DFT calculation, reaction mechanism was proposed.

Abstract Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of dramatically increases excited state oxidation...

We present a hollow-core fiber (HCF) based transient absorption experiment, with capabilities beyond common titanium:sapphire setups. By spectral filtering of the HCF spectrum, we provide pump pulses centered at 425 nm several hundred nJ pulse energy sample position. employing red edge output for seeding CaF2, obtain smooth probing spectra in range between 320 and 900 nm. demonstrate our experiment by following ultrafast relaxation dynamics radical cationic photocatalyst to prove its...

A mild carboamidation of electronically different styrenes with diverse hydrocarbons was developed by merging photocatalysis and electrochemistry without using external oxidants. The reaction proceeds through a tandem photocatalytic hydrogen atom transfer (HAT), radical addition to styrenes, polar crossover, subsequent Ritter-type amidation. Key engaging unactivated alkanes is the use tetrabutylammonium decatungstate (TBADT) as HAT photocatalyst, which regenerated from its reduced form...

Rhodium-catalyzed green synthesis of isoindolin-1-ones via a sequential C-H activation/allene formation/cyclization pathway by applying water as solvent is reported. The reaction highly regioselective, tolerating some potentially useful functional groups.

The first example of transition metal-catalyzed stereo-defined <italic>syn</italic>-β-OH elimination! A [Cp*RhCl₂]₂-catalyzed allenylation reaction available arenes with propargylic alcohols afforded fully substituted allenes excellent ees.

An efficient method for synthesis of polysubstituted cyclobutenones, which are not readily available from traditional methods due to the intrinsic ring strain, is described. The reaction 2,3-allenoates and organozinc reagents proceeds via a tandem Michael addition/cyclic 1,2-addition/elimination mechanism with functional groups being introduced 3-position cyclobutenone products regiospecifically in moderate excellent yields. Application stereodefined β,γ-unsaturated enones demonstrated.

Abstract Construction of two vicinal all-carbon quaternary carbon centres is great importance due to the common presence such units in natural and unnatural molecules with attractive functions. However, it remains a significant challenge. Here, we have developed palladium-catalysed general coupling for efficient connection tertiary atoms: Specifically, propargylic carbonate has been treated fully loaded soft functionalized nucleophile connect atoms simple palladium catalyst. It observed that...

A unique TfOH-catalyzed domino cycloisomerization/hydrolytic defluorination reaction of easily available<italic>n</italic>-perfluoroalkyl allenones in the presence H₂O providing furanyl perfluoroalkyl ketones has been developed.

Abstract Here, we describe that polymethylhydrosiloxane (PMHS) is a sustainable terminal reductant in the titanocene catalyzed hydrosilylation of epoxides. The products formally constitute anti ‐Markovnikov H 2 O‐addition to alkenes. PMHS not only more and cheaper than other silanes such as PhSiH 3 Ph(Me)SiH . It also results higher diastereoselectivity epoxide reduction.

An efficient TfOH- or AuCl-catalyzed cycloisomerization reaction of easily available<italic>n</italic>-perfluoroalkyl 1,2-allenyl ketones occurring smoothly to form 2-perfluoroalkyl furans 2-furyl perfluoroalkyl has been reported.

Four pieces were assembled by the reactions indicated, and dehydro precursor was semi-hydrogenated to give resolvin D1 (RvD1).

Abstract Die synthetische Photoelektrochemie (PEC) bietet neue Möglichkeiten für die Erzeugung und Handhabung reaktiver Zwischenstufen. Selektive Einelektronentransferreaktionen (SET) auf wesentlich umweltfreundlichere Weise Erweiterung des Redoxfensters erwecken Aufmerksamkeit. Dieser Aufsatz befasst sich mit den diesbezüglich neusten Beiträgen. Besprochen werden Kombination von PEC anderen Reaktivitäten (Wasserstoffatomtransfer, radical–polar crossover, Energietransfer‐Sensibilisierung),...

Electrochemically-mediated Photoredox Catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis the single electron transfer activation small organic molecules. However, mechanism how photoexcited radical ion species with ultrashort (picosecond-order) lifetimes could ever undergo productive photochemistry has eluded chemists. We report tri( para -substituted)biarylamines tunable class electroactivated...

Abstract Electron‐deficient acridones and in situ generated acridinium salts are reported as potent, closed‐shell photooxidants that undergo surprising mechanisms. When bridging acyclic triarylamine catalysts with a carbonyl group (acridones), this completely diverts their behavior away from open‐shell, radical cationic, ‘beyond diffusion’ photocatalysis to closed‐shell, neutral, diffusion‐controlled photocatalysis. Brønsted acid activation of dramatically increases excited state oxidation...

&lt;p&gt;Electrochemically-mediated Photoredox Catalysis emerged as a powerful synthetic technique in recent years, overcoming fundamental limitations of electrochemistry and photoredox catalysis the single electron transfer activation small organic molecules. However, mechanism how photoexcited radical ion species with ultrashort (picosecond-order) lifetimes could ever undergo productive photochemistry has eluded chemists. We report tri(&lt;i&gt;para&lt;/i&gt;-substituted)biarylamines...

Abstract This is the first example of a direct allenylation N‐methoxybenzamides with allenes.