Electrochemically Driven Dearomative Spirocyclization of Anisole-Based Cyclopropanols: Total Synthesis of Anhydro-β-rotunol.

An eco-friendly electrochemical oxidative dearomatization of anisole-based cyclopropyl alcohols has been developed for synthesizing spiro[4.5]diketones. The reaction involves the simultaneous C-C bond cleavage of cyclopropyl alcohols and spirocyclization with anisole under electrochemical conditions, eliminating the need for metal catalysts or additional oxidants.

Visible-Light-Induced Decarbonylative Truce-Smiles Rearrangement of -Sulfonylbenzamides.

A visible-light-induced decarbonylative Truce-Smiles rearrangement reaction of -allylbenzamides with diverse organohalides (R-X) is described, enabling efficient synthesis of β-phenethylamine derivatives in moderate to excellent yields. The chemoselectivity of decarbonylative rearrangement of -sulfonylbenzamides over desulfonation is featured through synergistic photoredox catalysis and water participation.

Photoredox/Bismuth Relay Catalysis Enabling Reductive Alkylation of Nitroarenes with Aldehydes.

The effective transition metal-free photoredox/bismuth dual catalytic reductive dialkylation of nitroarenes with benzaldehydes has been reported. The nitroarene reduction through visible light-driven photoredox catalysis was integrated with subsequent reductive dialkylation of anilines under bismuth catalysis to enable the cascade reductive alkylation of nitroarenes with carbonyls. Salient features of this relay catalysis system include mild reaction conditions, no requirement for transition metal catalysts, easy handling, step-economy, and high selectivity.

Chelation-Assisted Iron-Catalyzed C-H Activations: Scope and Mechanism.

ConspectusTo improve the resource economy of molecular syntheses, researchers have developed strategies to directly activate otherwise inert C-H bonds, thus avoiding cumbersome and costly substrate prefunctionalizations. During the past two decades, remarkable progress in coordination chemistry has set the stage for developing increasingly viable metal catalysts for C-H activations. Despite remarkable advances, C-H activations are largely dominated by precious 4d and 5d transition metal catalysts based primarily on palladium, ruthenium, iridium, and rhodium, thus decreasing the inherent sustainable nature of the C-H activation approach.

Misdiagnosis of scrotal and retroperitoneal lymphangioma in children.

Background: Scrotal and retroperitoneal lymphangioma (SRL) in children is relatively rare and its clinical symptoms are usually difficult to distinguish from other conditions such as hydrocele and incarcerated inguinal oblique hernia. This study aimed to explore the clinical diagnosis and treatment of abdominal scrotal lymphangioma in children, and thus, to increase our understandings of this disease in clinical practice.

Method: This study enrolled nine boys, aged 1-10, who were admitted to Shanghai Children's Hospital from January 2019 to December 2020 and who were finally confirmed with lymphangioma in the inguinal area.

Reduced peroxisome proliferator-activated receptor-α and bile acid nuclear receptor NR1H4/FXR may affect the hepatic immune microenvironment of biliary atresia.

Background: Biliary atresia (BA) is a childhood liver disease characterized by fibrous obstruction and obstruction of the extrahepatic biliary system and is one of the most common and serious biliary disorders in infants. Significant inflammation and fibrosis of the liver and biliary tract are the most prominent features, regardless of the initial damage to the BA. Abnormalities in innate or adaptive immunity have been found in human patients and mouse models of BA.

Iron-Catalyzed C-H Activation with Propargyl Acetates: Mechanistic Insights into Iron(II) by Experiment, Kinetics, Mössbauer Spectroscopy, and Computation.

An iron-catalyzed C-H/N-H alkyne annulation was realized by using a customizable clickable triazole amide under exceedingly mild reaction conditions. A unifying mechanistic approach combining experiment, spectroscopy, kinetics, and computation provided strong support for facile C-H activation by a ligand-to-ligand hydrogen transfer (LLHT) mechanism. Combined Mössbauer spectroscopic analysis and DFT calculations were indicative of high-spin iron(II) species as the key intermediates in the C-H activation manifold.

1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations.

Photo-induced copper-catalyzed C-H chalcogenation of azoles at room temperature.

Inexpensive copper catalysts enabled direct C-H chalcogenations at ambient temperature by means of photo-induced catalysis. The expedient copper catalysis set the stage for C-S and C-Se bond formation from readily accessible non-volatile elemental chalcogens. The photo-assisted copper catalysis manifold proved suitable for a wide range of substrates with good functional group tolerance and exhibited high catalytic efficacy even at a reaction temperature of 25 °C.

Rhodium(III)-Catalyzed C-H Activation/Alkyne Annulation by Weak Coordination of Peresters with O-O Bond as an Internal Oxidant.

A redox-economic strategy has been developed, involved in an efficient Rh(III)-catalyzed oxidative C-H activation and alkyne annulation with perester as the oxidizing directing group. In this process, the cleavage of an oxidizing O-O bond as an internal oxidant is described for the first time. This reaction could be carried out under mild conditions and exhibits excellent regioselectivity and wide functional groups tolerance.