Solvent Anions Enable Photoinduced Borylation and Phosphonation of Aryl Halides via EDA Complexes.

We report the synthesis of aryl boronic esters and aryl phosphonate esters promoted by visible-light in the absence of transition-metals or photoredox catalysts. The transformation proceeds at room temperature using sodium hydride, as a non-nucleophilic base, and exhibits functional group tolerance for anilines, amides, and esters. UV-vis spectroscopy, radical trapping experiments, and computational (TD-DFT) calculations suggest an electron-donor-acceptor (EDA) complex between solvent anions and aryl halides as the species responsible for this reactivity.

Photoinduced C(sp3)-H Chalcogenation of Amide Derivatives and Ethers via Ligand-to-Metal Charge-Transfer.

A photoinduced, iron(III) chloride-catalyzed C-H activation of N-methyl amides and ethers leads to the formation of C-S and C-Se bonds via a ligand-to-metal charge transfer (LMCT) process. This methodology converts secondary and tertiary amides, sulfonamides, and carbamates into the corresponding amido-N,S-acetal derivatives in good yields. Mechanistic work revealed that this transformation proceeds through a hydrogen atom transfer (HAT) involving chlorine radical intermediates.

Photoredox Polyfluoroarylation of Alkyl Halides via Halogen Atom Transfer.

Polyfluoroarene moieties are of interest in medicinal chemistry, agrochemicals, and material sciences. Herein, we present the first polyfluoroarylation of unactivated alkyl halides via a halogen atom transfer process. This method converts primary, secondary, and tertiary alkyl halides into the respective polyfluoroaryl compounds in good yields in the presence of amide, carbamate, ester, aromatic, and sulfonamide moieties, including derivatives of complex bioactive molecules. Mechanistic work revealed that this transformation proceeds through an alkyl radical generated after the halogen atom transfer.

Dimsyl Anion Enables Visible-Light-Promoted Charge Transfer in Cross-Coupling Reactions of Aryl Halides.

A methodology is reported for visible-light-promoted synthesis of unsymmetrical chalcogenides enabled by dimsyl anion in the absence of transition-metals or photoredox catalysts. The cross-coupling reaction between aryl halides and diaryl dichalcogenides proceeds with electron-rich, electron-poor, and heteroaromatic moieties. Mechanistic investigations using UV-Vis spectroscopy, time-dependent density functional theory (TD-DFT) calculations, and control reactions suggest that dimsyl anion forms an electron-donor-acceptor (EDA) complex capable of absorbing blue light, leading to a charge transfer responsible for generation of aryl radicals from aryl halides. This previously unreported mechanistic pathway may be applied to other light-induced transformations performed in DMSO in the presence of bases and aryl halides.

Transition-Metal-Free Photoredox Phosphonation of Aryl C-N and C-X Bonds in Aqueous Solvent Mixtures.

Herein, we present an efficient and mild methodology for the synthesis of aromatic phosphonate esters in good to excellent yields using 10H-phenothiazine, an inexpensive commodity chemical, as a photoredox catalyst. The reaction exhibits wide functional group compatibility enabling the transformation in the presence of ketone, amide, ester, amine, and alcohol moieties. Importantly, the reaction proceeds using a green solvent mixture primarily composed of water, thus lowering the environmental footprint of this transformation compared to current methods. The transformation also proceeds under atmospheric conditions, which further differentiates it from current methods that require inert atmosphere. Mechanistic work using fluorescence quenching experiments and radical trapping approaches support the proposed mechanism.

Photochemical Regioselective C(sp3)-H Amination of Amides Using N-Haloimides.

A metal-free regioselective C(sp3)-H amination of amides using N-haloimides in the presence of lithium tert-butoxide and visible light is presented herein. This photoexcited approach is straightforward, and it aminates a wide variety of amides under mild conditions without the use of photocatalysts, external radical initiators, or oxidants. A halogen-bonded intermediate between the tert-butoxide base and the N-haloimide is proposed to be responsible for the increased photoreactivity. Calculations show that the formation of this electron donor-acceptor complex presents an exergonic energy profile.

Metal-free visible-light-promoted C(sp3)-H functionalization of aliphatic cyclic ethers using trace O2.

Presented is a light-promoted C-C bond forming reaction yielding sulfone and phosphate derivatives at room temperature in the absence of metals or photoredox catalyst. This transformation proceeds in neat conditions through an auto-oxidation mechanism which is maintained through the leaching of trace amounts of O2 as sole green oxidant.

Photolysis, tautomerism and conformational analysis of dehydroacetic acid and a comparison with 2-hydroxyacetophenone and 2-acetyl-1,3-cyclohexanodione.

The purpose of this work was to determine the tautomerism, the conformational analysis and photoreactivity of dehydroacetic acid (DHAA, 1). For that reason, the photolysis of DHAA (1) was performed at 254 nm and compared with two structurally similar compounds: 2-hydroxyacetophenone (HAP, 2) and 2-acetyl-1,3-cyclohexanodione (ACH, 3). We confirmed the degradation of 1 to acetic acid and we propose a mechanism on the assumption that a [2+2] cyclodimerization occurs (after UV light absorption) followed by some consecutive Norrish Type I cleavages, affording ketenes that end-up in acetic acid. The UV absorption study was conducted for all three compounds to gain insight about their electronic transitions, both experimentally and with computational simulations using TDDFT (B3LYP/6-31+G(d,p)) methods. A detailed analysis of the different tautomers and isomers that can be present in solution and the MOs involved in the electronic transitions was also achieved. The HOMO→LUMO transition was the least energetic optically active transition for 1 and 2, whereas 3 was recognized to have a HOMO-1→LUMO transition. These transitions were all of n→π∗ character.

UV characterization and photodegradation mechanism of the fungicide chlorothalonil in the presence and absence of oxygen.

An experimental and theoretical study of the UV spectrum of chlorothalonil (CT) was carried out and the vibrationally resolved HOMO→LUMO transition is presented for the first time. The fluorescence spectrum has also been recorded. Furthermore, preparative photolysis allowed a detailed study of the photoproducts formed with recognition of different isomers. In the presence of oxygen only the first reductive dechlorination-decyanation occurred, while in its absence a successive dechlorination-decyanation takes place.

Histerectomia laparoscopica: resultado en 80 casos / Laparoscopic hysterectomy: result in 80 cases

En este trabajo referimos nuestra experiencia sobre histectomías laparoscópicas realizadas desde Agosto de 1992 hasta Mayo de 1994. Describimos el objetivo quirúrgico inicial y las variaciones en la técnica durante el mencionado período, tendiente a sistematizar el procedimiento. Disminuir el tiempo operatório de manera considerable: evitando complicaciones intra-operatorias. Enumeramos los diagnósticos pre-operatorios y su corroboración con los hallazgos histopatológicos. Evaluamos complicaciones intra-operatorias y post-operatorias. El tiempo qurúrgico; parámetro que sufrió variaciones significativas en el desarrollo de la técnica. La longitud de hospitalización y su calidad se mantuvieron con escasa relación al tiempo operatorio. Reconocemos una rápida incorporación de la mujer su completa actividad. Consideramos a la histerctomia laparoscópica como una alternativa válida en manos de un cirujano-endoscópico-ginecológo. Pensamos que este tipo de cirurgía representa una alternativa y una nueva forma de pensar (AU)

Histerectomia laparoscopica: resultado en 80 casos / Laparoscopic hysterectomy: result in 80 cases

En este trabajo referimos nuestra experiencia sobre histectomías laparoscópicas realizadas desde Agosto de 1992 hasta Mayo de 1994. Describimos el objetivo quirúrgico inicial y las variaciones en la técnica durante el mencionado período, tendiente a sistematizar el procedimiento. Disminuir el tiempo operatório de manera considerable: evitando complicaciones intra-operatorias. Enumeramos los diagnósticos pre-operatorios y su corroboración con los hallazgos histopatológicos. Evaluamos complicaciones intra-operatorias y post-operatorias. El tiempo qurúrgico; parámetro que sufrió variaciones significativas en el desarrollo de la técnica. La longitud de hospitalización y su calidad se mantuvieron con escasa relación al tiempo operatorio. Reconocemos una rápida incorporación de la mujer su completa actividad. Consideramos a la histerctomia laparoscópica como una alternativa válida en manos de un cirujano-endoscópico-ginecológo. Pensamos que este tipo de cirurgía representa una alternativa y una nueva forma de pensar