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The iridium-catalyzed C-H borylation of benzamides typically leads to meta and para selectivities using state-of-the-art iridium-based N , N -chelating bipyridine ligands. However, reaching ortho selectivity patterns requires extensive trial-and-error screening via molecular design at the ligand first coordination sphere. Herein, we demonstrate that triazolylpyridines are excellent ligands for the selective iridium-catalyzed ortho C-H borylation of tertiary benzamides and, importantly, we demonstrate the almost negligible effect of the first coordination sphere in the selectivity, which is so far unprecedented in iridium C-H bond borylations. Remarkably, the activity is dramatically enhanced by exploiting a remote Zn⋯O[double bond, length as m-dash]C weak interaction between the substrate and a rationally designed molecular-recognition site in the catalyst. Kinetic studies and DFT calculations indicate that the iridium-catalyzed C-H activation step is not rate-determining, this being unique for remotely controlled C-H functionalizations. Consequently, a previously established supramolecular iridium catalyst designed for meta -borylation of pyridines is now compatible with the ortho -borylation of benzamides, a regioselectivity switch that is counter-intuitive regarding precedents in the literature. In addition, we highlight the role of the cyclohexene additive in avoiding the formation of undesired side-products as well as accelerating the HBpin release event that precedes the catalyst regeneration step, which is highly relevant for the design of powerful and selective iridium borylating catalysts., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background: Burnout among emergency health care professionals is well-described, especially during the COVID-19 pandemic. Prevention interventions, such as mindfulness, focus on the management of stress., Objective: To evaluate the effects of the FIRECARE program (a mindfulness intervention, supplemented by heart coherence training and positive psychology workshops) on burnout, secondary stress, compassion fatigue, and mindfulness among advanced life support ambulance staff of the Paris Fire Brigade., Materials and Methods: We used a non-randomized, two-group quasi-experimental study design with a waitlist control and before-and-after measurements in each group. The intervention consisted of six, once-weekly, 2.5-h sessions that included individual daily meditation and cardiac coherence practice. The study compared intervention and waitlist control groups, and investigated baseline, post-program, and 3-month follow-up change on burnout (measuring using the ProQOL-5 scale) and mindfulness (measuring using the FMI scores). Baseline burnout (measured using the ProQOL-5) was evaluated and used in the analysis., Results: Seventy-four 74 participants volunteered to participate; 66 were included in the final analysis. Of these, 60% were classified as suffering from moderate burnout, the 'burnout cluster'. A comparison of intervention and waitlist control groups found a decrease in the burnout score in the burnout cluster ( p  = 0.0003; partial eta squared = 0.18). However, while secondary stress fell among the burnout cluster, it was only for participants in the intervention group; scores increased for those in the waitlist group ( p  = 0.003; partial eta squared = 0.12). The pre-post-intervention analysis of both groups also showed that burnout fell in the burnout cluster ( p  = 0.006; partial eta squared = 0.11). At 3-month follow-up, the burnout score was significantly reduced in the intervention group ( p  = 0.02; partial eta squared = 0.07), and both the acceptance ( p  = 0.007) and mindfulness scores ( p  = 0.05; partial eta squared = 0.05) were increased in the baseline burnout cluster., Conclusion: FIRECARE may be a useful approach to preventing and reducing burnout among prehospital caregivers.

The Wacker reaction is the oxidation of olefins to ketones and typically requires expensive and scarce palladium catalysts in the presence of an additional copper co-catalyst under harsh conditions (acidic media, high pressure of air/dioxygen, elevated temperatures). Such a transformation is relevant for industry, as shown by the synthesis of acetaldehyde from ethylene as well as for fine-chemicals, because of the versatility of a carbonyl group placed at specific positions. In this regard, many contributions have focused on controlling the chemo- and regioselectivity of the olefin oxidation by means of well-defined palladium catalysts under different sets of reaction conditions. However, the development of Wacker-type processes that avoid the use of palladium catalysts has just emerged in the last few years, thereby paving the way for the generation of more sustainable procedures, including milder reaction conditions and green chemistry technologies. In this Minireview, we discuss the development of new catalytic processes that utilize more benign catalysts and sustainable reaction conditions., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst that is able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C-H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent of the action modes of enzymes, new elementary catalytic steps (i. e. C-B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom-economy C-H bond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn⋅⋅⋅N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed C-H bond borylations with enzymatic Michaelis-Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns., (© 2021 Wiley-VCH GmbH.)

Homogeneous catalytic reactions are typically controlled by the stereoelectronic nature of the ligand(s) that bind to the metal(s). The advantages of the so-called first coordination sphere effects have been used for the efficient synthesis of fine chemicals relevant for industrial and academic laboratories since more than half a century. Such level of catalyst control has significantly upgraded in the last few decades by mastering additional interactions beyond the first coordination sphere. These so-called second coordination sphere effects are mainly inspired by the action mode of nature's catalysts, enzymes, and, in general, rely on subtle hydrogen bonding for the exquisite control of activity and selectivity. In order to span the scope of this powerful strategy to challenges that cannot be solved purely by hydrogen bonding, a variety of less common interactions have been successfully introduced in the last few years for a fine chemical synthesis. This review covers the latest and most exciting developments of this newly flourishing area with a particular focus on highlighting how these types of interactions can be rationally implemented to control the reactivity in a remote fashion, which is far away from the active site similar to what enzymes also do.

The institutional psychiatric treatment of migrant workers is difficult. But it is also necessary: the most dangerous evolutions happen when there is no intervention or during long breaks of therapy. From their own experience, authors ask themselves about what, in usual attitudes of psychiatrist, can drive into blind-alleys. The symptomatology shown by maghrebian migrant has implications in fields of sociology, culture and psychology, with wide extensions in politics, economics, etc. In front of symptoms (described there), different persons give different institutional answers, described too. Each pathological situation is either revelating of migrant's contradictions or origin of new contradictions.

Many people think that mental pathology connected with maghrebian migration into France is coming from a psychopathology more or less specific to migration and maghrebian origin. But, the migrant worker, when sick, asks directly or not the question of his own identity. Authors insist on obligation to take in count the sociological, psychological and cultural characteristics of migrant's problems, and also the ways of changing concerning both his own imago and his relationship to others. The concept of identity gives us facility to integrate all these elements.